CN114165797A - Catalytic combustion treatment method for chlorine-containing organic waste gas - Google Patents
Catalytic combustion treatment method for chlorine-containing organic waste gas Download PDFInfo
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- CN114165797A CN114165797A CN202111361019.5A CN202111361019A CN114165797A CN 114165797 A CN114165797 A CN 114165797A CN 202111361019 A CN202111361019 A CN 202111361019A CN 114165797 A CN114165797 A CN 114165797A
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- chlorine
- catalytic combustion
- waste gas
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- 239000007789 gas Substances 0.000 title claims abstract description 82
- 239000000460 chlorine Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 74
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 64
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 57
- 239000010815 organic waste Substances 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 293
- 238000001179 sorption measurement Methods 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 20
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical group [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 95
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- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
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- 229960002089 ferrous chloride Drugs 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
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- 239000012494 Quartz wool Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
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- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000006227 byproduct Substances 0.000 abstract description 9
- 231100000572 poisoning Toxicity 0.000 abstract description 9
- 230000000607 poisoning effect Effects 0.000 abstract description 9
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- 238000010438 heat treatment Methods 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 2
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- 239000000243 solution Substances 0.000 description 106
- 238000002360 preparation method Methods 0.000 description 50
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 32
- 239000002244 precipitate Substances 0.000 description 32
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 32
- 239000002002 slurry Substances 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 229910000510 noble metal Inorganic materials 0.000 description 18
- 239000011651 chromium Substances 0.000 description 17
- 238000007598 dipping method Methods 0.000 description 17
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 16
- 238000000975 co-precipitation Methods 0.000 description 16
- 239000012065 filter cake Substances 0.000 description 16
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 16
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- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
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- 238000002485 combustion reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 8
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- 239000010949 copper Substances 0.000 description 7
- 229940050176 methyl chloride Drugs 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
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- 239000002912 waste gas Substances 0.000 description 3
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- -1 and CO is high2 Substances 0.000 description 1
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- 238000004056 waste incineration Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/56—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
- F23G2209/142—Halogen gases, e.g. silane
-
- 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
Abstract
The invention discloses a catalytic combustion treatment method for chlorine-containing organic waste gas, which solves the problems of incomplete oxidation, catalyst poisoning, generation of highly toxic byproducts, high cost and the like in the catalytic combustion treatment of the chlorine-containing organic waste gas. The method comprises the steps of treating chlorine-containing organic waste gas, introducing the treated chlorine-containing organic waste gas into an active carbon adsorption bed for adsorption, and switching the active carbon adsorption bed after adsorption saturation; heating air by a heater, then feeding the heated air into a saturated activated carbon adsorption bed for desorption treatment, heating the desorbed gas, and then feeding the heated gas into a catalytic combustion reactor for catalytic combustion reaction; wherein the catalytic combustion reactor is filled with a catalyst A, a blocking medium and a catalyst B; the catalyst A is a catalyst for catalyzing and combusting chlorine-containing VOCs; the catalystThe agent B is an HCl oxidation catalyst. The method is simple, and the conversion rate and Cl are high2High selectivity, low investment and running cost, long service life of catalyst and equipment, and recoverable by-product.
Description
Technical Field
The invention relates to an organic waste gas treatment method, in particular to a chlorine-containing organic waste gas catalytic combustion treatment method.
Background
In recent years, volatile organic compounds have become one of the main sources of atmospheric pollution. Among volatile organic compounds, chlorine-containing volatile organic compounds have the characteristics of high toxicity, high treatment difficulty and the like, and become a difficult point for treatment. The chlorine-containing volatile organic compounds are important chemical raw materials and widely exist in industrial production of petrochemical industry, fine chemical industry and the like. Meanwhile, a large amount of chlorine-containing organic waste gas is generated in the processes of waste incineration and the like, so that the human health and the ecological environment are endangered.
For the treatment of chlorine-containing organic waste gas, the currently adopted main treatment technologies comprise adsorption method, combustion method, catalytic combustion method, biodegradation method and the like. The adsorption method is suitable for organic waste gas with single component and higher concentration, and can be recycled. For organic waste gas with complex components and low recovery value, the adsorbent becomes hazardous waste after being adsorbed and saturated, and the treatment difficulty is increased. The regenerative combustion method has good treatment effect, but has higher investment and higher operation cost. The biodegradation method has low treatment cost, but has poor adaptability, and the strain has high requirement on the environment and cannot resist the impact of working condition change. Compared with other technologies, the catalytic combustion method has the advantages of low treatment temperature, low energy consumption, high applicability, no secondary pollution and the like, and has wide application prospect in the field of treating chlorine-containing volatile organic compounds.
The catalyst is the core for catalytic combustion of chlorine-containing organic waste gas, and the noble metal catalysts, composite oxide catalysts and perovskite catalysts are mainly used in the prior application and research. The noble metal catalyst mostly uses Pt and Pd as active components, has high reaction activity, but HCl and the like generated by degradation are easy to form noble metal chloride to cause catalyst poisoning, and on the other hand, the noble metal is expensive and also limits the noble metal chlorideApplication is carried out. The improvement of the chlorine poisoning resistance of the noble metal catalyst and the reduction of the loading amount of the noble metal in the catalyst become important researches on the noble metal catalyst. Studies of Zhulianli et al (petrochemical, 2010,39(4):449-453) show that the halogen poisoning resistance of the Pt-Pd noble metal catalyst can be remarkably improved by adding a small amount of non-noble metal auxiliary agent, but the catalyst has high noble metal content and the cost is not obviously reduced. Compared with Pt and Pd, the noble metal Ru has lower price and stronger halogen poisoning resistance. CN105126834A discloses a noble metal ruthenium catalyst for catalytic combustion of PTA tail gas, which is obtained by molding a powder catalyst, and the carrier is ZrO2、Al2O3、SiO2Or rutile phase TiO modified by ZnO2. The catalyst has low reaction temperature and high catalytic activity, but the loading capacity of ruthenium is higher, the cost of the catalyst is high, and the catalyst is difficult to popularize and apply on a large scale. The activity of the composite oxide catalyst and the perovskite catalyst developed aiming at chlorine-containing organic waste gas can be close to the level of a noble metal catalyst, the catalyst is low in cost, but short in service life, high in comprehensive use cost and low in industrial application. Patent CN103894200A discloses a catalyst of Fe, Ni, Cr, Bi or Mn doped cobaltosic oxide, which can catalyze and combust chlorinated aromatic hydrocarbon efficiently, but has lower strength and is only suitable for waste gas treatment at lower space velocity.
The catalytic oxidation mechanisms for chlorine-containing VOCs are generally C-Cl, C-H bond scission, and deep oxidation of C-containing byproducts, i.e., dechlorination, preliminary oxidation, and deep oxidation. The existing catalyst is generally a one-stage catalyst, has the functions of dechlorination and oxidation, and has the problems of incomplete oxidation, catalyst poisoning and generation of high-toxicity byproducts in long-term operation. In the existing catalytic combustion method, HCl generated by combustion is mostly absorbed by an alkali liquor method. On one hand, HCl is corrosive to the pipes, and on the other hand, the alkali absorption method consumes alkali liquor, which increases the treatment cost.
Disclosure of Invention
The invention aims to solve the technical problems and provides a method which is simple, has good treatment efficiency, high conversion rate of chlorine-containing organic waste gas, low equipment investment and operation cost, long service life of a catalyst and equipment, no waste gas or waste water discharge, by-product recovery, continuous operation, high efficiency, low energy consumption and low operation cost.
The technical scheme is that chlorine-containing organic waste gas is introduced into an active carbon adsorption bed for adsorption after being treated by a preprocessor, and the active carbon adsorption bed is switched after the adsorption is saturated; heating air by a heater, then feeding the heated air into a saturated activated carbon adsorption bed for desorption treatment, heating desorbed gas led out after desorption treatment by a heat exchanger and a preheater in sequence, and then feeding the desorbed gas into a catalytic combustion reactor for catalytic combustion reaction; tail gas discharged from the catalytic combustion reactor exchanges heat with the thermally desorbed gas through a heat exchanger, enters a spray tower for absorption and is discharged;
the catalytic combustion reactor is sequentially filled with a catalyst A, a blocking medium and a catalyst B from an air inlet to an air outlet;
the catalyst A is a catalyst for catalyzing and combusting chlorine-containing VOCs; the blocking medium is at least one of quartz sand, alumina, quartz wool and glass fiber; the catalyst B is an HCl oxidation catalyst.
The active components of the catalyst A are Cr, Mn and Cu, the molar ratio is 0.5-1:3-4:0.5-1, the first carrier of the catalyst A is a composite oxide of Ce, Zr and Al, the molar ratio is 3-5:1-2:2-4, and the second carrier is cordierite honeycomb ceramic;
the active components of the catalyst B are Ru, Ce and Mn with the molar ratio of 1-2:1-3:4-8, and the first carrier of the catalyst B is rutile phase TiO2、ZrO2、SnO2The molar ratio is 6-8:0.5-1:0.5-1, and the second carrier is cordierite honeycomb ceramic.
In the catalyst A and the catalyst B, the active components account for 2-10 wt% of the first carrier, more preferably 5-10 wt% of the catalyst A, and more preferably 2-5 wt% of the catalyst B; the first carriers each account for 10 to 30 wt%, more preferably 15 to 25 wt%, of the mass fraction of the second carrier.
The preparation method of the catalyst A comprises the following steps:
dissolving Ce, Zr and Al precursors in deionized water, and adding a precipitator Na2CO3Or NaOH, aging, filtering, washing, drying at 60-120 deg.C for 8-12h, and calcining at 350-650 deg.C for 3-6h to obtain a first carrier composite oxide;
preparing nitrate solution of Cr, Mn and Cu, adding the first carrier, drying at 60-120 ℃ for 8-12h, and roasting at 350-650 ℃ for 3-6h to obtain a powder catalyst A;
adding water and a nonionic surfactant into the powder catalyst A, preparing a coating solution after ball milling, soaking a second carrier cordierite honeycomb ceramic into the coating solution, drying, roasting, weighing, and repeating the coating process at least once to obtain the catalyst A.
The preparation method of the catalyst B comprises the following steps:
dissolving Zr and Al precursors in deionized water, and adding anatase TiO2Filtering, washing, drying at 60-120 deg.c for 8-12 hr, and roasting at 650 deg.c for 3-6 hr to obtain the first composite carrier oxide;
preparing nitrate solution of Ru, Mn and Ce, adding the first carrier, drying at 60-120 ℃ for 8-12h, and roasting at 350-650 ℃ for 3-6h to obtain a powder catalyst B;
adding water and a nonionic surfactant into the powder catalyst B, preparing a coating solution after ball milling, soaking a second carrier cordierite honeycomb ceramic into the coating solution, drying, roasting, weighing, and repeating the coating process at least once to obtain the catalyst B.
The packing volume ratio of the catalyst A blocking medium to the catalyst B is 1: 0.1-0.5: 0.1-0.5. The temperature of the catalytic reaction in the catalytic combustion reactor is controlled to be 300-400 ℃, and the space velocity of the desorbed gas is controlled to be 1000-200000h-1。
And the absorption liquid in the spray tower is ferrous chloride solution.
Iron chips or iron sheets are filled on the tower plate below the liquid level in the spray tower.
In view of the problems in the background art, the inventor makes the following improvements:
(1) the catalytic combustion reactor adopted by the invention is filled with two-stage catalyst, the first stage catalyst A contains chlorineMost of the engine exhaust gas is degraded into CO2And HCl, Cr and Cu are introduced into the Mn-based catalyst as auxiliaries, wherein Cr has strong catalytic oxidation capacity and can improve the chlorine poisoning resistance of the catalyst, Cu can modulate the active center on the surface of the catalyst and improve the oxidation capacity of the Mn-based catalyst, and the addition of Cr and Cu improves the oxidation performance of the whole catalyst, so that most of Cl is oxidized into chlorine. Preferably, the molar ratio of Cr, Mn and Cu in the active component in the catalyst A is 0.5-1:3-4:0.5-1, the stability of the catalyst is affected by excessively high addition amount of Cr, the cost of the catalyst is increased, and the poisoning performance of the catalyst is deteriorated by excessively low addition amount of Cr; too high or too low an amount of Cu added may degrade the oxidation performance of the catalyst.
Further, in the second-stage catalyst B, Mn and Ce are introduced to modify the Ru catalyst, wherein Mn can improve the oxidation performance of the catalyst, Ce can improve the distribution of active centers on the surface of the catalyst and improve the oxidation activity, the addition of Ce and Mn obviously reduces the using amount of noble metal Ru, and HCl is further oxidized into Cl by the second-stage catalyst B2The corrosion of HCl direct discharge on the device is overcome, and the further degradation of intermediate byproducts and the complete oxidation of CO are ensured. Compared with the traditional one-stage catalyst, the dosage of the noble metal Ru can be reduced by 40-60% under the same unit gas treatment amount, and the total catalyst cost can be reduced. Preferably, Ru, Ce and Mn are selected, the molar ratio is 1-2:1-3:4-8, when the addition amount of Ce is too high, the activity of the catalyst is basically unchanged, and when the addition amount of Ce is too low, the oxidation performance of the catalyst is reduced; too high and too low addition of Mn both reduce the oxidation performance of the catalyst.
In conclusion, the two-stage catalyst in the reactor can meet the space velocity of 1000--1The treatment requirement of chlorine-containing organic waste gas (desorbed gas, the concentration of chlorine-containing VOCs can reach 3000ppm at most), the conversion rate of the chlorine-containing organic waste gas and CO2High selectivity, longer service life and good stability, and solves the problems of incomplete oxidation, catalyst poisoning and generation of highly toxic byproducts in the one-stage catalyst.
(2) In the preparation process of the catalyst A and the catalyst B, when the powder type catalyst is prepared, a nonionic surfactant is introduced, preferably at least one of polyvinyl alcohol, tween or polyethylene glycol, the nonionic surfactant can reduce the surface tension, increase the coating amount and improve the strength and stability of the catalyst, the addition amount of the nonionic surfactant is 5-10 wt% of the mass of the powder type catalyst, the strength of the catalyst is influenced too much, and the loading amount of the catalyst is influenced too little.
(3) Two sections of catalysts are filled in one reactor, the middle of the two sections of catalysts are separated by a barrier medium, the catalytic reaction temperature is similar, the control is easy, the gas can continuously pass through one reactor to carry out two catalytic reactions in sequence, the gas treatment capacity is large, the stability is good, and the overhaul and the maintenance are easy.
(4) Based on the adoption of the catalytic combustion reactor, after two-stage catalytic treatment, HCl is further oxidized into Cl2The corrosion of HCl on the device is overcome, and the further degradation of the intermediate by-products is ensured; at the moment, the chlorine is recovered by using the ferrous chloride solution soaked with the iron filings or iron pieces in the spray tower, so that the waste can be effectively changed into valuable, and the method can be used for sewage treatment or preparation of polymer-grade ferric trichloride.
(5) The method is simple, has good treatment efficiency, and has the advantages of high conversion rate of the chlorine-containing organic waste gas and Cl2High selectivity, low equipment investment and operation cost, long service life of the catalyst and the equipment, no waste gas and waste water discharge, capability of recycling byproducts, continuous operation, high efficiency, low energy consumption, low operation cost and environmental protection.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
FIG. 2 is a graph showing the results of the experiment in example 1 of the present invention.
Wherein, the pretreatment device comprises 1-a preprocessor, 2-an active carbon adsorption bed, 3-an electric heater, 4-a heat exchanger, 5-a catalytic combustion reactor, 6-an exhaust fan, 7-a spray tower, 8-a centrifugal pump, 9-a liquid storage tank, 10-a main exhaust fan, 11-a chimney and 12-a preheater.
Detailed Description
Example 1:
preparation of catalyst a:
pretreatment of a second carrier cordierite honeycomb ceramic: and (3) putting the cordierite honeycomb ceramic carrier into dilute nitric acid with the mass concentration of 5% to be soaked for 2h, then washing the cordierite honeycomb ceramic carrier for 3 times by using deionized water, and drying the cordierite honeycomb ceramic carrier for 10h at the temperature of 120 ℃ to obtain the cordierite honeycomb ceramic with the activated surface.
Preparation of the first carrier: the carrier is prepared by adopting a coprecipitation method, 1L of mixed solution of 0.2mol/L cerium nitrate, 0.075mol/L zirconium nitrate and 0.15mol/L aluminum nitrate is measured, sodium carbonate solution with the mass concentration of 2 wt% is dropwise added while stirring at the temperature of 80 ℃, the pH value of the solution is maintained at 10, the solution is continuously stirred for 8 hours, the aging is carried out for 12 hours, then the filtration is carried out, and the precipitate is washed by deionized water until the precipitate becomes neutral. And drying the filter cake at 110 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the CeZrAl carrier, wherein the ratio of Ce: zr: the molar ratio of Al is 4:1.5: 3.
Preparation of powder catalyst: 50mL of 0.128mol/L chromium nitrate solution, 100mL of 0.256mol/L manganese nitrate solution, 50mL of 0.128mol/L copper nitrate solution and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of CeZrAl carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the CrMnCu/CeZrAl powder type catalyst, wherein the content of active components accounts for 8 wt% of the first carrier, and the molar ratio of Cr: mn: cu 1:4: 1.
Preparing an integral catalyst: 40g of powder catalyst is put into a ball milling tank, 4g of polyvinyl alcohol and 116g of water are added, and ball milling is carried out for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, blow-drying the slurry remained in the pore channel, drying the cordierite honeycomb ceramic for 12h at the temperature of 110 ℃, roasting the cordierite honeycomb ceramic for 5h at the temperature of 550 ℃, and repeating the coating process until the powder catalyst accounts for 20 percent of the mass of the second carrier to obtain the CrMnCu/CeZrAl honeycomb ceramic monolithic catalyst, namely the catalyst A.
Preparation of catalyst B:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by coprecipitation and mixing method, a mixed solution of 1L0.035mol/L zirconium nitrate and 0.07mol/L tin nitrate is measured, 33.6g anatase TiO is added2And (3) dropwise adding a sodium carbonate solution with the mass concentration of 2 wt% into the powder while stirring at the temperature of 80 ℃, maintaining the pH value of the solution to be 10, continuously stirring for 8 hours, aging for 12 hours, then carrying out suction filtration, and washing the precipitate with deionized water until the precipitate becomes neutral. Drying the filter cake at 110 deg.C for 12h, calcining at 500 deg.C for 5h, and mixing the obtained carrier powder with the above TiO2：ZrO2：SnO2The molar ratio was 6:0.5: 1.
Preparation of powder catalyst: 50mL of a 0.04mol/L ruthenium nitrate solution, 50mL of a 0.04mol/L cerium nitrate solution, 100mL of a 0.128mol/L manganese nitrate solution, and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of TiZrSn carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the RuCeMn/TiZrSn powder type catalyst, wherein the content of active components accounts for 3% of the mass of the first carrier, and the molar ratio of Ru: ce: mn is 1:1: 4.
Preparing an integral catalyst: 40g of powder catalyst is put into a ball milling tank, 4g of polyvinyl alcohol and 116g of water are added, and ball milling is carried out for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, blow-drying the slurry remained in the pore channel, drying the cordierite honeycomb ceramic for 12h at the temperature of 110 ℃, roasting the cordierite honeycomb ceramic for 5h at the temperature of 550 ℃, and repeating the coating process until the powder catalyst accounts for 20 percent of the mass of the second carrier to obtain the RuCeMn/TiZrSn honeycomb ceramic monolithic catalyst, namely the catalyst B.
The combustion treatment method comprises the following steps:
chlorine-containing organic waste gas (volume content) discharged from a certain chemical plant: methyl chloride 50ppm, methylene chloride 200ppm, chlorobenzene 50 ppm.
After being treated by a preprocessor 1, chlorine-containing organic waste gas is introduced into an active carbon adsorption bed 2 for adsorption (one active carbon adsorption bed 2 is used for standby), the active carbon adsorption bed for standby is switched after adsorption is saturated, and purified gas after adsorption is discharged from a flue 11 through a main exhaust fan 10;
air is heated by a heater 3 and then sent into a saturated activated carbon adsorption bed 2 for desorption treatment, desorbed gas led out after desorption treatment is heated by a heat exchanger 4 and a preheater 12 in sequence and then is introduced into a catalytic combustion reactor 5 for catalytic combustion reaction, and desorbed gas is desorbed in the catalytic combustion reactor 5The latter gas reacts with the catalyst A (catalyst A layer 5.1) filled at the upper section to degrade most of the chlorine-containing VOCs in the gas into CO2、Cl2And HCl; then the reaction product is reacted with a catalyst B (catalyst B layer 5.3) at the lower section after passing through a barrier medium (barrier medium layer 5.2) at the middle section, and a small amount of HCl left in the gas is further oxidized into Cl2And deeply oxidizing and removing residual trace chlorine-containing VOCs. The tail gas discharged from the catalytic combustion reactor 5 exchanges heat with the desorbed gas through the heat exchanger 4, enters the spray tower 7 through the desorption fan 6 to be washed and recycled, is finally led out from the top of the tower and is discharged from the flue 11 through the main exhaust fan 10.
Wherein the absorption liquid in the spray tower is ferrous chloride solution, the tower plate below the liquid level in the spray tower is filled with iron chips or iron sheets, and the absorption liquid discharged from the bottom of the tower is sent into a liquid storage tank 9 and then sent into the top of the tower through a centrifugal pump 8 for circulating spraying.
The filling volume ratio of the catalyst a, the blocking medium and the catalyst B in the catalytic combustion reactor 5 is 1: 0.1: 0.2, controlling the catalytic reaction temperature in the catalytic combustion reactor 5 to be 350 ℃, and using quartz sand as a blocking medium.
After desorption, the gas space velocity is 15000h-1Under the condition, the conversion rate of the chlorine-containing organic waste gas and Cl2The selectivity, outlet chloride concentration are shown in table 1.
Example 2
Preparation of catalyst a:
pretreatment of a second carrier cordierite honeycomb ceramic: the same pretreatment method as that for the second carrier cordierite honeycomb ceramic used in catalyst A of example 1 was employed.
Preparation of the first carrier: the carrier is prepared by adopting a coprecipitation method, 1L of mixed solution of 0.2mol/L cerium nitrate, 0.1mol/L zirconium nitrate and 0.15mol/L aluminum nitrate is measured, sodium carbonate solution with the mass concentration of 2 wt% is dropwise added while stirring at the temperature of 80 ℃, the pH value of the solution is maintained at 10, the stirring is continued for 8 hours, the aging is carried out for 12 hours, then the filtration is carried out, and the precipitate is washed by deionized water until the precipitate becomes neutral. And drying the filter cake at 110 ℃ for 12h, and roasting at 550 ℃ for 5h to obtain the CeZrAl carrier, wherein the ratio of Ce: zr: the molar ratio of Al is 4:2: 3.
Preparation of powder catalyst: 50mL of 0.128mol/L chromium nitrate solution, 100mL of 0.328mol/L manganese nitrate solution, 50mL of 0.082mol/L copper nitrate solution and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of CeZrAl carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the CrMnCu/CeZrAl powder type catalyst, wherein the content of active components accounts for 9 wt% of the first carrier, and the molar ratio of Cr: mn: cu is 0.8:4: 0.5.
Preparing an integral catalyst: 40g of powder catalyst is put into a ball milling tank, 4g of polyvinyl alcohol and 156g of water are added, and ball milling is carried out for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 20%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, blow-drying the slurry remained in the pore channel, drying the cordierite honeycomb ceramic for 12h at the temperature of 110 ℃, roasting the cordierite honeycomb ceramic for 5h at the temperature of 550 ℃, and repeating the coating process until the powder catalyst accounts for 18 percent of the mass of the second carrier to obtain the CrMnCu/CeZrAl honeycomb ceramic monolithic catalyst, namely the catalyst A.
Preparation of catalyst B:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by adopting a coprecipitation and blending method, a mixed solution of 1L0.075mol/L zirconium nitrate and 0.038mol/L tin nitrate is measured, and 36g of anatase TiO is added2And (3) dropwise adding a sodium carbonate solution with the mass concentration of 2 wt% into the powder while stirring at the temperature of 80 ℃, maintaining the pH value of the solution to be 10, continuously stirring for 8 hours, aging for 12 hours, then carrying out suction filtration, and washing the precipitate with deionized water until the precipitate becomes neutral. Drying the filter cake at 110 deg.C for 12h, calcining at 550 deg.C for 5h, and mixing the obtained carrier powder with the above TiO2：ZrO2：SnO2The molar ratio was 6:1: 0.5.
Preparation of powder catalyst: 50mL of a 0.02mol/L ruthenium nitrate solution, 50mL of a 0.04mol/L cerium nitrate solution, 100mL of a 0.04mol/L manganese nitrate solution, and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of TiZrSn carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the RuCeMn/TiZrSn powder type catalyst, wherein the content of active components accounts for 2% of the mass of the first carrier, and the molar ratio of Ru: ce: mn ═ 1:2: 4.
Preparing an integral catalyst: putting 40g of powder catalyst into a ball milling tank, adding 4g of Tween and 116g of water, and carrying out ball milling for 2h to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, blow-drying the slurry remained in the pore channel, drying the cordierite honeycomb ceramic for 12h at the temperature of 110 ℃, roasting the cordierite honeycomb ceramic for 5h at the temperature of 550 ℃, and repeating the coating process until the powder catalyst accounts for 25 percent of the mass of the second carrier to obtain the RuCeMn/TiZrSn honeycomb ceramic monolithic catalyst, namely the catalyst B.
The combustion treatment method comprises the following steps:
chlorine-containing organic waste gas discharged from a certain chemical plant: methyl chloride 50ppm, methylene chloride 200ppm, chlorobenzene 50 ppm.
The treatment method was the same as in example 1, except that:
the filling volume ratio of the catalyst a, the blocking medium and the catalyst B in the catalytic combustion reactor 5 is 1: 0.2: 0.15, the blocking medium is quartz wool, and the catalytic reaction temperature in the catalytic combustion reactor 5 is controlled to be 350 ℃.
After desorption, the gas space velocity is 15000h-1Under the condition, the conversion rate of the chlorine-containing organic waste gas and Cl2The selectivity, outlet chloride concentration are shown in table 1.
Example 3
Preparing a catalyst:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by adopting a coprecipitation method, 1L of mixed solution of 0.2mol/L cerium nitrate, 0.08mol/L zirconium nitrate and 0.08mol/L aluminum nitrate is measured, sodium hydroxide solution with the mass concentration of 2 wt% is dropwise added while stirring at the temperature of 80 ℃, the pH value of the solution is maintained to be 10, the stirring is continued for 8 hours, the aging is carried out for 12 hours, then the filtration is carried out, and the precipitate is washed by deionized water until the precipitate becomes neutral. And drying the filter cake at 110 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the CeZrAl carrier, wherein the ratio of Ce: zr: the molar ratio of Al is 5:2: 2.
Preparation of powder catalyst: 50mL of 0.128mol/L chromium nitrate solution, 100mL of 0.256mol/L manganese nitrate solution, 50mL of 0.128mol/L copper nitrate solution and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of CeZrAl carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the CrMnCu/CeZrAl powder type catalyst, wherein the content of active components accounts for 8 wt% of the first carrier, and the molar ratio of Cr: mn: cu 1:4: 1.
Preparing an integral catalyst: putting 40g of powder catalyst into a ball milling tank, adding 4g of Tween and 116g of water, and carrying out ball milling for 2h to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, blow-drying the slurry remained in the pore channel, drying the cordierite honeycomb ceramic for 12h at the temperature of 110 ℃, roasting the cordierite honeycomb ceramic for 5h at the temperature of 550 ℃, and repeating the coating process until the powder catalyst accounts for 25 percent of the mass of the second carrier to obtain the CrMnCu/CeZrAl honeycomb ceramic monolithic catalyst, namely the catalyst A.
Preparation of catalyst B:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by coprecipitation and mixing method, 1L0.055mol/L zirconium nitrate and 0.055mol/L tin nitrate mixed solution is measured, 35.2g anatase TiO anatase is added2And (3) dropwise adding a sodium hydroxide solution with the mass concentration of 2 wt% into the powder while stirring at the temperature of 80 ℃, maintaining the pH value of the solution to be 10, continuously stirring for 8 hours, aging for 12 hours, then carrying out suction filtration, and washing the precipitate with deionized water until the precipitate becomes neutral. Drying the filter cake at 110 deg.C for 12h, calcining at 500 deg.C for 5h, and mixing the obtained carrier powder with the above TiO2：ZrO2：SnO2The molar ratio is 8:1: 1.
Preparation of powder catalyst: 50mL of a 0.07mol/L ruthenium nitrate solution, 50mL of a 0.07mol/L cerium nitrate solution, 50mL of a 0.21mol/L manganese nitrate solution, and 200mL of deionized water were measured to prepare an impregnation solution. Adding 40g of TiZrSn carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the RuCeMn/TiZrSn powder type catalyst, wherein the content of active components accounts for 4% of the mass of the first carrier, and the molar ratio of Ru: ce: mn is 1:1: 3.
Preparing an integral catalyst: 40g of powder catalyst is put into a ball milling tank, 4g of polyvinyl alcohol and 116g of water are added, and ball milling is carried out for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, blow-drying the slurry remained in the pore channel, drying the cordierite honeycomb ceramic for 12h at the temperature of 110 ℃, roasting the cordierite honeycomb ceramic for 5h at the temperature of 550 ℃, and repeating the coating process until the powder catalyst accounts for 20 percent of the mass of the second carrier to obtain the RuCeMn/TiZrSn honeycomb ceramic monolithic catalyst, namely the catalyst B.
The combustion treatment method comprises the following steps:
chlorine-containing organic waste gas discharged from a certain chemical plant: methyl chloride 50ppm, methylene chloride 200ppm, chlorobenzene 50 ppm.
The treatment method was the same as in example 1, except that:
the filling volume ratio of the catalyst a, the blocking medium and the catalyst B in the catalytic combustion reactor 5 is 1: 0.2: 0.2, the separation medium is alumina, the catalytic reaction temperature in the catalytic combustion reactor 5 is controlled to be 350 ℃, and the gas reaction space velocity after desorption is 20000h-1。
Conversion rate of chlorine-containing organic waste gas, Cl2The selectivity, outlet chloride concentration are shown in table 1.
Example 4
Preparing a catalyst:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by adopting a coprecipitation method, 1L of mixed solution of 0.21mol/L cerium nitrate, 0.07mol/L zirconium nitrate and 0.14mol/L aluminum nitrate is measured, sodium carbonate solution with the mass concentration of 2 wt% is dropwise added under the stirring at the temperature of 80 ℃, the pH value of the solution is maintained at 10, the stirring is continued for 8 hours, the aging is carried out for 12 hours, then the filtration is carried out, and the precipitate is washed by deionized water until the precipitate becomes neutral. And drying the filter cake at 110 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the CeZrAl carrier, wherein the ratio of Ce: zr: the molar ratio of Al is 3:1: 2.
Preparation of powder catalyst: 50mL of a 0.16mol/L chromium nitrate solution, 100mL of a 0.32mol/L manganese nitrate solution, 50mL of a 0.16mol/L copper nitrate solution, and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of CeZrAl carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 6h at 650 ℃ to obtain the CrMnCu/CeZrAl powder type catalyst, wherein the content of active components accounts for 10 wt% of the first carrier, and the molar ratio of Cr: mn: cu 1:4: 1.
Preparing an integral catalyst: putting 40g of powder catalyst into a ball milling tank, adding 4g of polyethylene glycol and 116g of water, and carrying out ball milling for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, blow-drying the slurry remained in the pore channel, drying the cordierite honeycomb ceramic for 12h at the temperature of 110 ℃, roasting the cordierite honeycomb ceramic for 5h at the temperature of 550 ℃, and repeating the coating process until the powder catalyst accounts for 25 percent of the mass of the second carrier to obtain the CrMnCu/CeZrAl honeycomb ceramic monolithic catalyst, namely the catalyst A.
Preparation of catalyst B:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by coprecipitation and mixing method, 1L0.032mol/L zirconium nitrate and 0.032mol/L tin nitrate mixed solution is measured, 41.6g anatase TiO anatase is added2And (3) dropwise adding a sodium carbonate solution with the mass concentration of 2 wt% into the powder while stirring at the temperature of 80 ℃, maintaining the pH value of the solution to be 10, continuously stirring for 8 hours, aging for 12 hours, then carrying out suction filtration, and washing the precipitate with deionized water until the precipitate becomes neutral. Drying the filter cake at 110 deg.C for 12h, calcining at 500 deg.C for 5h, and mixing the obtained carrier powder with the above TiO2：ZrO2：SnO2The molar ratio was 8:0.5: 0.5.
Preparation of powder catalyst: 50mL of a 0.04mol/L ruthenium nitrate solution, 50mL of a 0.12mol/L cerium nitrate solution, 100mL of a 0.08mol/L manganese nitrate solution, and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of TiZrSn carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the RuCeMn/TiZrSn powder type catalyst, wherein the content of active components accounts for 5% of the mass of the first carrier, and the molar ratio of Ru: ce: mn ═ 1:3: 4.
Preparing an integral catalyst: putting 40g of powder catalyst into a ball milling tank, adding 4g of polyethylene glycol and 116g of water, and carrying out ball milling for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, drying the slurry remained in the pore channel by blowing, drying the slurry at 110 ℃ for 12h, roasting the slurry at 650 ℃ for 5h, and repeating the coating process until the powder catalyst accounts for 25% of the mass of the second carrier to obtain the RuCeMn/TiZrSn honeycomb ceramic monolithic catalyst, namely the catalyst B.
The combustion treatment method comprises the following steps:
chlorine-containing organic waste gas discharged from a certain chemical plant: methyl chloride 50ppm, methylene chloride 200ppm, chlorobenzene 50 ppm.
The treatment method was the same as in example 1, except that:
the filling volume ratio of the catalyst a, the blocking medium and the catalyst B in the catalytic combustion reactor 5 is 1: 0.2: 0.1, the barrier medium is glass fiber, the catalytic reaction temperature in the catalytic combustion reactor 5 is controlled to be 400 ℃, and the gas reaction space velocity after desorption is 15000h-1。
Conversion rate of chlorine-containing organic waste gas, Cl2The selectivity, outlet chloride concentration are shown in table 1.
Example 5
Preparing a catalyst:
preparation of catalyst a:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by adopting a coprecipitation method, 1L of mixed solution of 0.2mol/L cerium nitrate, 0.08mol/L zirconium nitrate and 0.16mol/L aluminum nitrate is measured, sodium carbonate solution with the mass concentration of 2 wt% is dropwise added under the stirring at the temperature of 80 ℃, the pH value of the solution is maintained at 10, the stirring is continued for 8 hours, the aging is carried out for 12 hours, then the filtration is carried out, and the precipitate is washed by deionized water until the precipitate becomes neutral. And drying the filter cake at 110 ℃ for 12h, and roasting at 550 ℃ for 5h to obtain the CeZrAl carrier, wherein the ratio of Ce: zr: the molar ratio of Al is 5:2: 4.
Preparation of powder catalyst: 50mL of 0.104mol/L chromium nitrate solution, 100mL of 0.208mol/L manganese nitrate solution, 50mL of 0.052mol/L copper nitrate solution and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of CeZrAl carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the CrMnCu/CeZrAl powder type catalyst, wherein the content of active components accounts for 6 wt% of the first carrier, and the molar ratio of Cr: mn: cu 1:4: 0.5.
Preparing an integral catalyst: 40g of powder catalyst is put into a ball milling tank, 4g of polyvinyl alcohol and 116g of water are added, and ball milling is carried out for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, drying the slurry remained in the pore channel by blowing, drying the slurry at 110 ℃ for 12h, roasting the slurry at 400 ℃ for 5h, and repeating the coating process until the powder catalyst accounts for 15% of the mass of the second carrier to obtain the CrMnCu/CeZrAl honeycomb ceramic monolithic catalyst, namely the catalyst A.
Preparation of catalyst B:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by coprecipitation and mixing method, 1L0.06mol/L zirconium nitrate and 0.06mol/L tin nitrate mixed solution is measured, 33.6g anatase TiO is added2And (3) dropwise adding a sodium carbonate solution with the mass concentration of 2 wt% into the powder while stirring at the temperature of 80 ℃, maintaining the pH value of the solution to be 10, continuously stirring for 8 hours, aging for 12 hours, then carrying out suction filtration, and washing the precipitate with deionized water until the precipitate becomes neutral. Drying the filter cake at 110 deg.C for 12h, calcining at 500 deg.C for 5h, and mixing the obtained carrier powder with the above TiO2：ZrO2：SnO2The molar ratio was 7:1: 1.
Preparation of powder catalyst: 50mL of 0.025mol/L ruthenium nitrate solution, 50mL of 0.075mol/L cerium nitrate solution, 100mL of 0.1mol/L manganese nitrate solution and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of TiZrSn carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the RuCeMn/TiZrSn powder type catalyst, wherein the content of active components accounts for 4% of the mass of the first carrier, and the molar ratio of Ru: ce: mn is 1:3: 8.
Preparing an integral catalyst: 40g of powder catalyst is put into a ball milling tank, 4g of polyvinyl alcohol and 116g of water are added, and ball milling is carried out for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 20%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, drying the slurry remained in the pore channel by blowing, drying the slurry at 110 ℃ for 12h, roasting the slurry at 350 ℃ for 5h, and repeating the coating process until the powder catalyst accounts for 15% of the mass of the second carrier to obtain the RuCeMn/TiZrSn honeycomb ceramic monolithic catalyst, namely the catalyst B.
The combustion treatment method comprises the following steps:
chlorine-containing organic waste gas discharged from a certain chemical plant: methyl chloride 200ppm, methylene chloride 100 ppm.
The treatment method was the same as in example 1, except that:
the filling volume ratio of the catalyst a, the blocking medium and the catalyst B in the catalytic combustion reactor 5 is 1: 0.2: 0.3, the barrier medium is quartz sand, the catalytic reaction temperature in the catalytic combustion reactor 5 is controlled to be 300 ℃, and the gas reaction space velocity after desorption is 20000h-1。
Conversion rate of chlorine-containing organic waste gas, Cl2The selectivity, outlet chloride concentration are shown in table 1.
Example 6
Preparing a catalyst:
preparation of catalyst a:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by adopting a coprecipitation method, 1L of mixed solution of 0.21mol/L cerium nitrate, 0.07mol/L zirconium nitrate and 0.21mol/L aluminum nitrate is measured, sodium carbonate solution with the mass concentration of 2 wt% is dropwise added under the stirring at the temperature of 80 ℃, the pH value of the solution is maintained at 10, the stirring is continued for 8 hours, the aging is carried out for 12 hours, then the filtration is carried out, and the precipitate is washed by deionized water until the precipitate becomes neutral. And drying the filter cake at 110 ℃ for 12h, and roasting at 650 ℃ for 5h to obtain the CeZrAl carrier, wherein the ratio of Ce: zr: the molar ratio of Al is 3:1: 3.
Preparation of powder catalyst: 50mL of a 0.096mol/L chromium nitrate solution, 100mL of a 0.288mol/L manganese nitrate solution, 50mL of a 0.192mol/L copper nitrate solution, and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of CeZrAl carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the CrMnCu/CeZrAl powder type catalyst, wherein the content of active components accounts for 9 wt% of the first carrier, and the molar ratio of Cr: mn: cu is 0.5:3: 1.
Preparing an integral catalyst: putting 40g of powder catalyst into a ball milling tank, adding 4g of Tween and 116g of water, and carrying out ball milling for 2h to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, drying the slurry remained in the pore channel by blowing, drying the cordierite honeycomb ceramic for 12h at 110 ℃, roasting the cordierite honeycomb ceramic for 3h at 650 ℃, and repeating the coating process until the powder catalyst accounts for 15% of the mass of the second carrier to obtain the CrMnCu/CeZrAl honeycomb ceramic monolithic catalyst, namely the catalyst A.
Preparation of catalyst B:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by coprecipitation and mixing method, 1L0.066mol/L zirconium nitrate and 0.033mol/L tin nitrate mixed solution is measured, 37.3g anatase TiO is added2And (3) dropwise adding a sodium carbonate solution with the mass concentration of 2 wt% into the powder while stirring at the temperature of 80 ℃, maintaining the pH value of the solution to be 10, continuously stirring for 8 hours, aging for 12 hours, then carrying out suction filtration, and washing the precipitate with deionized water until the precipitate becomes neutral. Drying the filter cake at 110 deg.C for 12h, calcining at 500 deg.C for 5h, and mixing the obtained carrier powder with the above TiO2：ZrO2：SnO2The molar ratio was 7:1: 0.5.
Preparation of powder catalyst: 50mL of 0.072mol/L ruthenium nitrate solution, 50mL of 0.11mol/L cerium nitrate solution, 100mL of 0.073mol/L manganese nitrate solution and 150mL of deionized water are measured to prepare a dipping solution. Adding 40g of TiZrSn carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the RuCeMn/TiZrSn powder type catalyst, wherein the content of active components accounts for 5% of the mass of the first carrier, and the molar ratio of Ru: ce: mn is 2:3: 4.
Preparing an integral catalyst: putting 40g of powder catalyst into a ball milling tank, adding 4g of Tween and 116g of water, and carrying out ball milling for 2h to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, drying the slurry remained in the pore channel by blowing, drying the slurry at 110 ℃ for 12h, roasting the slurry at 350 ℃ for 5h, and repeating the coating process until the powder catalyst accounts for 15% of the mass of the second carrier to obtain the RuCeMn/TiZrSn honeycomb ceramic monolithic catalyst, namely the catalyst B.
The combustion treatment method comprises the following steps:
chlorine-containing organic waste gas discharged from a certain chemical plant: methyl chloride 100ppm, methylene chloride 150ppm, chlorobenzene 100 ppm.
The treatment method was the same as in example 1, except that:
the filling volume ratio of the catalyst a, the blocking medium and the catalyst B in the catalytic combustion reactor 5 is 1: 0.5:0.5, the barrier medium is quartz wool, the catalytic reaction temperature in the catalytic combustion reactor 5 is controlled to be 300 ℃, and the gas reaction space velocity after desorption is 20000h-1。
Conversion rate of chlorine-containing organic waste gas, Cl2The selectivity, outlet chloride concentration are shown in table 1.
Example 7
Preparing a catalyst:
preparation of catalyst a:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by adopting a coprecipitation method, 1L of mixed solution of 0.2mol/L cerium nitrate, 0.05mol/L zirconium nitrate and 0.2mol/L aluminum nitrate is measured, sodium carbonate solution with the mass concentration of 2 wt% is dropwise added under the stirring at the temperature of 80 ℃, the pH value of the solution is maintained at 10, the stirring is continued for 8 hours, the aging is carried out for 12 hours, then the filtration is carried out, and the precipitate is washed by deionized water until the precipitate becomes neutral. And drying the filter cake at 110 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the CeZrAl carrier, wherein the ratio of Ce: zr: the molar ratio of Al is 4:1: 4.
Preparation of powder catalyst: 50mL of 0.106mol/L chromium nitrate solution, 100mL of 0.159mol/L manganese nitrate solution, 50mL of 0.053mol/L copper nitrate solution and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of CeZrAl carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the CrMnCu/CeZrAl powder type catalyst, wherein the content of active components accounts for 5 wt% of the first carrier, and the molar ratio of Cr: mn: cu 1:3: 0.5.
Preparing an integral catalyst: 40g of powder catalyst is put into a ball milling tank, 4g of polyvinyl alcohol and 116g of water are added, and ball milling is carried out for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, drying the slurry remained in the pore channel by blowing, drying the slurry at 110 ℃ for 12h, roasting the slurry at 350 ℃ for 6h, and repeating the coating process until the powder catalyst accounts for 15% of the mass of the second carrier to obtain the CrMnCu/CeZrAl honeycomb ceramic monolithic catalyst, namely the catalyst A.
Preparation of catalyst B:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by coprecipitation and blending method, 1L of mixed solution of 0.041mol/L zirconium nitrate and 0.041mol/L tin nitrate is measured, 39.6g of anatase TiO is added2And (3) dropwise adding a sodium hydroxide solution with the mass concentration of 2 wt% into the powder while stirring at the temperature of 80 ℃, maintaining the pH value of the solution to be 10, continuously stirring for 8 hours, aging for 12 hours, then carrying out suction filtration, and washing the precipitate with deionized water until the precipitate becomes neutral. Drying the filter cake at 110 deg.C for 12h, calcining at 500 deg.C for 5h, and mixing the obtained carrier powder with the above TiO2：ZrO2：SnO2The molar ratio was 6:0.5: 0.5.
Preparation of powder catalyst: 50mL of a 0.054mol/L ruthenium nitrate solution, 50mL of a 0.08mol/L cerium nitrate solution, 100mL of a 0.068mol/L manganese nitrate solution, and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of TiZrSn carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the RuCeMn/TiZrSn powder type catalyst, wherein the content of active components accounts for 4% of the mass of the first carrier, and the molar ratio of Ru: ce: mn is 2:3: 5.
Preparing an integral catalyst: 40g of powder catalyst is put into a ball milling tank, 4g of polyvinyl alcohol and 116g of water are added, and ball milling is carried out for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, drying the slurry remained in the pore channel by blowing, drying the slurry at 110 ℃ for 12h, roasting the slurry at 650 ℃ for 5h, and repeating the coating process until the powder catalyst accounts for 15% of the mass of the second carrier to obtain the RuCeMn/TiZrSn honeycomb ceramic monolithic catalyst, namely the catalyst B.
The combustion treatment method comprises the following steps:
chlorine-containing organic waste gas discharged from a certain chemical plant: 60ppm of methyl chloride, 130ppm of dichloromethane and 120ppm of chlorobenzene
The treatment method was the same as in example 1, except that:
the filling volume ratio of the catalyst a, the blocking medium and the catalyst B in the catalytic combustion reactor 5 is 1: 0.5: 0.2, the barrier medium is glass fiber, the catalytic reaction temperature in the catalytic combustion reactor 5 is controlled to be 300 ℃, and the gas reaction space velocity after desorption is 10000h-1。
Conversion rate of chlorine-containing organic waste gas, Cl2The selectivity, outlet chloride concentration are shown in table 1.
Example 8
Preparing a catalyst:
preparation of catalyst a:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by adopting a coprecipitation method, 1L of mixed solution of 0.2mol/L cerium nitrate, 0.04mol/L zirconium nitrate and 0.08mol/L aluminum nitrate is measured, sodium carbonate solution with the mass concentration of 2 wt% is dropwise added under the stirring at the temperature of 80 ℃, the pH value of the solution is maintained at 10, the stirring is continued for 8 hours, the aging is carried out for 12 hours, then the filtration is carried out, and the precipitate is washed by deionized water until the precipitate becomes neutral. And drying the filter cake at 110 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the CeZrAl carrier, wherein the ratio of Ce: zr: the molar ratio of Al is 5:1: 2.
Preparation of powder catalyst: 50mL of a 0.12mol/L chromium nitrate solution, 100mL of a 0.36mol/L manganese nitrate solution, 50mL of a 0.12mol/L copper nitrate solution, and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of CeZrAl carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 550 ℃ to obtain the CrMnCu/CeZrAl powder type catalyst, wherein the content of active components accounts for 10 wt% of the first carrier, and the molar ratio of Cr: mn: cu is 0.5:3: 0.5.
Preparing an integral catalyst: 40g of powder catalyst is put into a ball milling tank, 4g of polyvinyl alcohol and 116g of water are added, and ball milling is carried out for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, blow-drying the slurry remained in the pore channel, drying the cordierite honeycomb ceramic for 12h at the temperature of 110 ℃, roasting the cordierite honeycomb ceramic for 5h at the temperature of 550 ℃, and repeating the coating process until the powder catalyst accounts for 20 percent of the mass of the second carrier to obtain the CrMnCu/CeZrAl honeycomb ceramic monolithic catalyst, namely the catalyst A.
Preparation of catalyst B:
pretreatment of a second carrier cordierite honeycomb ceramic:
the same method as that for pretreating the second carrier cordierite honeycomb ceramic in the catalyst a of example 1 was used.
Preparation of the first carrier: the carrier is prepared by coprecipitation and mixing method, 1L0.06mol/L zirconium nitrate and 0.03mol/L tin nitrate mixed solution is measured, 38.6g anatase TiO anatase is added2And (3) dropwise adding a sodium carbonate solution with the mass concentration of 2 wt% into the powder while stirring at the temperature of 80 ℃, maintaining the pH value of the solution to be 10, continuously stirring for 8 hours, aging for 12 hours, then carrying out suction filtration, and washing the precipitate with deionized water until the precipitate becomes neutral. Drying the filter cake at 110 deg.C for 12h, calcining at 650 deg.C for 5h, and mixing the obtained carrier powder with the above TiO2：ZrO2：SnO2The molar ratio was 8:1: 0.5.
Preparation of powder catalyst: 50mL of a 0.036mol/L ruthenium nitrate solution, 50mL of a 0.108mol/L cerium nitrate solution, 100mL of a 0.108mol/L manganese nitrate solution, and 150mL of deionized water were measured to prepare an impregnation solution. Adding 40g of TiZrSn carrier, stirring and dipping for 4h, then drying for 10h at 110 ℃ in a drying oven, and finally roasting for 5h at 650 ℃ to obtain the RuCeMn/TiZrSn powder type catalyst, wherein the content of active components accounts for 5% of the mass of the first carrier, and the molar ratio of Ru: ce: mn ═ 1:3: 6.
Preparing an integral catalyst: 40g of powder catalyst is put into a ball milling tank, 4g of polyvinyl alcohol and 116g of water are added, and ball milling is carried out for 2 hours to prepare coating liquid, wherein the solid content in the coating liquid is 25%. And (3) immersing the cordierite honeycomb ceramic into the coating liquid for 30min, taking out the cordierite honeycomb ceramic, blow-drying the slurry remained in the pore channel, drying the cordierite honeycomb ceramic for 12h at the temperature of 110 ℃, roasting the cordierite honeycomb ceramic for 5h at the temperature of 550 ℃, and repeating the coating process until the powder catalyst accounts for 25 percent of the mass of the second carrier to obtain the RuCeMn/TiZrSn honeycomb ceramic monolithic catalyst, namely the catalyst B.
The combustion treatment method comprises the following steps:
chlorine-containing organic waste gas discharged from a certain chemical plant: 40ppm of methyl chloride, 60ppm of dichloromethane and 100ppm of chlorobenzene.
The treatment method was the same as in example 1, except that:
the filling volume ratio of the catalyst a, the blocking medium and the catalyst B in the catalytic combustion reactor 5 is 1: 0.1: 0.1, the barrier medium is quartz wool, the catalytic reaction temperature in the catalytic combustion reactor 5 is controlled to be 400 ℃, and the gas reaction space velocity after desorption is 10000h-1。
Conversion rate of chlorine-containing organic waste gas, Cl2The selectivity, outlet chloride concentration are shown in table 1.
Comparative example 1
The reactor was filled with catalyst A alone, otherwise as in example 1.
Comparative example 2
The reactor was filled with catalyst B alone, otherwise as in example 1.
Comparative example 3
The tail gas recovery adopts alkali liquor spraying, and the rest is the same as the example 1.
Comparative example 4
The reactor was charged with only conventional Ru catalyst (CN 105126834B), the same as a in example 1, except as in example 1.
TABLE 1 Chloro-organic waste gas catalytic combustion treatment System-related data
As can be seen from the experimental data in Table 1, the catalyst and the catalytic combustion treatment method of the present invention have high conversion rate of VOCs containing chlorine, and CO is high2、Cl2High selectivity and low discharge of chloride. Combining the results of example 1 and comparative examples 1 and 2, it can be seen that each index of the dual catalyst combination is significantly better than that of the single catalysts a and B. By combining the results of the example 1 and the comparative example 3, it can be known that each index of the ferrous chloride tail gas recovery system is similar to the performance of the alkali liquor spraying system. The discharge amount of chloride is less than 5.8mg/m in a 1000-hour life test3Conversion of chlorine-containing organic waste gas and CO2The selectivity is higher than 99.5 percent, and the selectivity of chlorine is about 89 percent. The recovery rate of chlorine (converted into ferrous chloride) is more than 95%. Combining the results of example 1 and comparative example 4, it can be seen that the amount of Ru in example 1 is only 0.5% of the mass of the powder catalyst, the amount of Ru supported in comparative example 4 is 1% of the mass of the powder catalyst, and at the same time, the noble metal B catalyst in example 1 is only 20% of the volume ratio of the composite metal catalyst a, so the noble metal demand of the composite catalyst is greatly reduced, and the cost is significantly reduced. Compared with the single catalytic oxidation of the chlorine-containing VOCs disclosed by the patent, the combined catalyst has obvious advantages in each index, wherein the combination of the double catalysts can mainly oxidize chlorine species into chlorine gas, is beneficial to reacting with waste scrap iron to generate polymer-grade ferric chloride, realizes the comprehensive utilization of the chlorine species and changes waste into valuable.
Claims (9)
1. A chlorine-containing organic waste gas catalytic combustion processing method, chlorine-containing organic waste gas is introduced into an activated carbon adsorption bed for adsorption after being processed by a preprocessor, and the activated carbon adsorption bed is switched after the adsorption is saturated; the method is characterized in that gas led out after desorption treatment is heated by a heat exchanger and a preheater in sequence and then is led into a catalytic combustion reactor for catalytic combustion reaction; tail gas discharged by the catalytic combustion reactor exchanges heat with the desorbed gas through a heat exchanger, enters a spray tower for absorption and is discharged;
the catalytic combustion reactor is sequentially filled with a catalyst A, a blocking medium and a catalyst B from an air inlet to an air outlet;
the catalyst A is a catalyst for catalyzing and combusting chlorine-containing VOCs; the blocking medium is at least one of quartz sand, alumina, quartz wool and glass fiber; the catalyst B is an HCl oxidation catalyst.
2. The catalytic combustion treatment method of chlorine-containing organic waste gas according to claim 1, wherein the active components of the catalyst A are Cr, Mn and Cu, the molar ratio is 0.5-1:3-4:0.5-1, the first carrier of the catalyst A is a composite oxide of Ce, Zr and Al, the molar ratio is 3-5:1-2:2-4, and the second carrier is cordierite honeycomb ceramic;
the active components of the catalyst B are Ru, Ce and Mn with the molar ratio of 1-2:1-3:4-8, and the first carrier of the catalyst B is rutile phase TiO2、ZrO2、SnO2The molar ratio is 6-8:0.5-1:0.5-1, and the second carrier is cordierite honeycomb ceramic.
3. The catalytic combustion processing method for chlorine-containing organic waste gas as claimed in claim 2, wherein the active components of the catalyst A and the catalyst B respectively account for 2-10 wt% of the mass fraction of the first carrier, and the mass fraction of the first carrier and the mass fraction of the second carrier respectively account for 10-30 wt%.
4. The catalytic combustion treatment method for chlorine-containing organic waste gas according to claim 2 or 3, wherein the catalyst A is prepared by the following steps:
dissolving Ce, Zr and Al precursors in deionized water, and adding a precipitator Na2CO3Or NaOH, aging, filtering, washing, drying at 60-120 deg.C for 8-12h, and calcining at 350-650 deg.C for 3-6h to obtain the first carrier composite oxide；
Preparing nitrate solution of Cr, Mn and Cu, adding the first carrier, drying at 60-120 ℃ for 8-12h, and roasting at 350-650 ℃ for 3-6h to obtain a powder catalyst A;
adding water and a nonionic surfactant into the powder catalyst A, preparing a coating solution after ball milling, soaking a second carrier cordierite honeycomb ceramic into the coating solution, drying, roasting, weighing, and repeating the coating process at least once to obtain the monolithic catalyst A.
5. The catalytic combustion treatment method for chlorine-containing organic waste gas according to claim 2 or 3, wherein the catalyst B is prepared by the following steps:
dissolving Zr and Sn precursors in deionized water, and adding anatase TiO2Filtering, washing, drying at 60-120 deg.c for 8-12 hr, and roasting at 650 deg.c for 3-6 hr to obtain the first composite carrier oxide;
preparing nitrate solution of Ru, Mn and Ce, adding the first carrier, drying at 60-120 ℃ for 8-12h, and roasting at 350-650 ℃ for 3-6h to obtain a powder catalyst B;
adding water and a nonionic surfactant into the powder catalyst B, preparing a coating solution after ball milling, soaking a second carrier cordierite honeycomb ceramic into the coating solution, drying, roasting, weighing, and repeating the coating process at least once to obtain the catalyst B.
6. The catalytic combustion treatment method for chlorine-containing organic waste gas as claimed in any one of claims 1 to 3, wherein the packing volume ratio of the catalyst A barrier medium to the catalyst B is 1: 0.1-0.5: 0.1-0.5.
7. The catalytic combustion treatment method for chlorine-containing organic waste gas as claimed in any of claims 1-3, wherein the catalytic reaction temperature in the catalytic combustion reactor is controlled to be 300--1。
8. The catalytic combustion treatment method for chlorine-containing organic waste gas as claimed in any one of claims 1 to 3, wherein the absorption liquid in the spray tower is ferrous chloride solution.
9. The catalytic combustion treatment method of chlorine-containing organic waste gas as claimed in claim 1, wherein iron chips or iron flakes are packed on the tray below the liquid level in the spray tower.
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| CN101637725A (en) * | 2009-08-20 | 2010-02-03 | 浙江工业大学 | Honeycomb ceramic type monolithic catalyst using mayenite as coating layer, preparation method and application thereof |
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| CN109381964A (en) * | 2018-09-28 | 2019-02-26 | 中科天龙（厦门）环保股份有限公司 | Organic exhaust gas recovery and processing system and method |
| CN110038608A (en) * | 2019-04-25 | 2019-07-23 | 中国科学院金属研究所 | A kind of structured catalyst material and the application in VOCs catalyticing combustion process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023228889A1 (en) * | 2022-05-25 | 2023-11-30 | 株式会社レゾナック | Chlorine gas-decomposing catalyst and exhaust gas treatment device |
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