CN111229245A - Organic chlorine-containing waste gas treating agent, preparation method and application thereof - Google Patents
Organic chlorine-containing waste gas treating agent, preparation method and application thereof Download PDFInfo
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- CN111229245A CN111229245A CN201911419132.7A CN201911419132A CN111229245A CN 111229245 A CN111229245 A CN 111229245A CN 201911419132 A CN201911419132 A CN 201911419132A CN 111229245 A CN111229245 A CN 111229245A
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- treating agent
- waste gas
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- organic chlorine
- chlorine
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 68
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000460 chlorine Substances 0.000 title claims abstract description 60
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 60
- 239000002912 waste gas Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 43
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 32
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 11
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 8
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910001868 water Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004537 pulping Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 28
- 239000001569 carbon dioxide Substances 0.000 abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 14
- 230000000382 dechlorinating effect Effects 0.000 abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 10
- 230000007062 hydrolysis Effects 0.000 abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 10
- 238000006298 dechlorination reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 5
- 239000001110 calcium chloride Substances 0.000 abstract description 5
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 5
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000012744 reinforcing agent Substances 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 150000004045 organic chlorine compounds Chemical class 0.000 abstract description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 8
- 229940117389 dichlorobenzene Drugs 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- -1 methane hydrocarbon Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 150000001555 benzenes Chemical class 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010298 TiOSO4 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides a treating agent for waste gas containing low-concentration organic chlorine, a preparation method and application thereof, wherein the treating agent takes light calcium carbonate as a main component, oxides of iron, manganese and titanium are added, fibrous calcium sulfate is taken as a reinforcing agent, the treating agent has higher organic chlorine hydrolysis activity and organic component combustion activity, and dechlorination of an organic chlorine compound and catalytic combustion of a byproduct chlorine-free organic component are realized under the temperature condition of 300-350 ℃, so that organic chlorine is converted into calcium chloride, carbon dioxide and water, the standard discharge is easy to realize, and the organic chlorine conversion capacity and the dechlorination capacity of the treating agent are not influenced by the carbon dioxide contained in the waste gas; the raw materials used by the dechlorinating agent are cheap, the cost of the dechlorinating agent is low, the dechlorinating agent is basically non-toxic after being used and is easy to scrap and treat. The organic chlorine-containing waste gas treating agent is prepared from raw materials including, by mass, 60-80 parts of light calcium carbonate, 10-15 parts of ferrous sulfate, 5-10 parts of manganese sulfate and 5-15 parts of metatitanic acid.
Description
Technical Field
The invention belongs to the technical field of organic chlorine-containing waste gas treatment, and particularly relates to a treatment agent for organic chlorine-containing waste gas, a preparation method and application thereof.
Background
Chlorine-containing organic matters, also called organic chlorine, are important industrial raw materials, such as chlorine-containing alkane and chlorine-containing aromatic hydrocarbon, and are widely used as raw materials and solvents for chemical reactions or addition components of a plurality of processing aids; because of its volatility, difficult degradability and toxicity, organic chlorine in waste gas, waste liquor and waste material can be properly treated, converted and removed, and can be discharged, treated or buried; the treatment of the organic chlorine in the waste gas is the most important technical field, and the organic chlorine in the waste liquid and the waste material is driven into the waste gas through gas stripping and thermal volatilization for treatment, so that the treatment is often convenient and easy to carry out.
When the content of organic chloride in the waste gas is high, the separation and utilization of the organic chloride are a treatment way; the organic chlorine is subjected to hydrogenation treatment, the generated hydrogen chloride which is easy to remove is converted and treated effectively, and the by-product is nontoxic or utilizable hydrocarbon. However, in many cases, the concentration of organic chlorine in the exhaust gas is low, and therefore it is inconvenient to treat and utilize the organic chlorine by a separation method, or the low-concentration gas obtained after most of the organic chlorine is separated is treated by catalytic combustion, and therefore, the method is sometimes economically effective. In the catalytic combustion process, organic chlorine is firstly subjected to catalytic hydrolysis, generally, the organic chlorine is hydrolyzed to generate hydrogen chloride which is easy to remove, and a byproduct of chlorine-free organic matter which can be catalytically combusted is further oxidized to generate carbon dioxide and water, wherein the two processes can be completed step by step or synchronously realized, and usually are realized at a proper temperature such as 200-500 ℃ and under the conditions of a catalyst and a treating agent with proper performances, wherein the catalytic hydrolysis of the organic chlorine needs to have a proper alkaline active site.
For chlorine, e.g. 500mg/m3Or the following common organic chlorine-containing waste gas is treated at 400 ℃ such as 250 ℃ and is convenient and easy to implement in many cases by adopting a dechlorinating agent which takes calcium oxide as a main component and is added with oxides such as iron, manganese, copper and the like, the chlorine in the organic chlorine can be converted into calcium chloride to be trapped in the dechlorinating agent, but the treated waste gas still contains chlorine-free organic matters which exceed the standardThe waste water cannot reach the standard and is discharged, or further treatment is needed to reach the standard; and when the waste gas contains carbon dioxide, calcium oxide is converted into non-alkaline calcium carbonate, or the waste gas is stored for a long time to absorb the carbon dioxide, so that the organic chlorine conversion capability of the dechlorinating agent is reduced and the dechlorinating capacity is reduced. Some copper-containing dechlorinations may also result in the production of higher chlorine containing organochlorines or increase the complexity of the organochlorines.
Disclosure of Invention
In order to solve the technical problems, the invention provides a treating agent for waste gas containing low-concentration organic chlorine and a preparation method thereof, the treating agent takes light calcium carbonate as a main component, oxides of iron, manganese and titanium are added, fibrous calcium sulfate is taken as a reinforcing agent, and the treating agent has higher organic chloride hydrolysis activity and organic component combustion activity, the dechlorination of the organic chlorine compound and the catalytic combustion of the byproduct chlorine-free organic component are realized under the temperature condition of 300-350 ℃, therefore, the organic chlorine is converted into calcium chloride, carbon dioxide and water, the discharge reaching the standard is easy to realize, the organic chlorine conversion capacity and dechlorination capacity of the treating agent are not influenced by the carbon dioxide contained in the waste gas, and the treating agent is basically non-toxic and easy to scrap and treat when the treating agent loses efficacy after use and comprises the calcium chloride, calcium carbonate which is not converted, and oxides of iron, manganese and titanium and calcium sulfate. The raw materials used by the treating agent are cheap, the cost of the treating agent is low, and the long-term storage performance is unchanged.
The organic chlorine-containing waste gas treating agent is prepared from raw materials including, by mass, 60-80 parts of light calcium carbonate, 10-15 parts of ferrous sulfate, 5-10 parts of manganese sulfate and 5-15 parts of metatitanic acid.
The preparation method of the organic chlorine-containing waste gas treating agent comprises the following steps:
A. adding 80-100 parts of water into a reaction kettle, adding all ferrous sulfate and manganese sulfate, stirring to dissolve, adding metatitanic acid, pulping, gradually adding light calcium carbonate powder for reaction, heating to 80-95 ℃, taking pH3-4 as a feeding reaction control end point of the light calcium carbonate powder, maintaining the reaction temperature and pH value range, and aging for 2-3hr to prepare slurry containing calcium sulfate fibers;
B. adding the rest light calcium carbonate powder into a kneader, adding sesbania powder, uniformly mixing, gradually spraying the slurry containing the calcium sulfate fibers, kneading, and extruding strips;
C. drying the extruded strip, and calcining at 420-450 deg.C in air for 2-4hr to obtain the final product.
The metatitanic acid is preferably an intermediate material in the production process of titanium dioxide by a sulfuric acid method, 3.5-5m% of sulfuric acid is generally burnt at 1150 ℃, 78-83% of titanium dioxide is burnt, the contained sulfuric acid is converted into calcium sulfate, and most of the sulfuric acid is fibrous and plays a role in enhancing.
The ferrous sulfate is preferably ferrous sulfate heptahydrate which is a byproduct of a titanium dioxide device in a sulfuric acid method, the purity of the ferrous sulfate is about 90%, and the contained sulfate of titanium and manganese is converted into oxides in the preparation process of the treating agent.
The light calcium carbonate has an average particle size of 1-3 μm and a specific surface area of 3-6m2The amount is preferably in the case of/g, and when too coarse, contact with the other components is insufficient, and when too fine, the strength of the treating agent is lowered.
The main component of the treating agent of the invention is CaCO in mass content355-70%，Fe2O35-7%，MnO2.3-5%, TiO25-7% of calcium sulfate and 13-22% of calcium sulfate; at the temperature of 350 ℃ and the space velocity of 100 ℃ for 1000hr-1For example containing chlorine, e.g. 500mg/m3Or Fe contained in the following common organic chlorine-containing waste gas treatment process2O3、TiO2Has large hydrolysis effect on organic chlorine, wherein TiO2The catalytic hydrolysis of (2) requires active sites with appropriate basicity, MnO, TiO2The method plays a main role in burning the byproduct chlorine-free organic matters and a small amount of chlorine-free organic matters contained in the waste gas; consuming O in the tail gas during the combustion process2Some Fe before dechlorination failure or penetration2O3MnO is generated into chloride; CaCO3Is a quasi-in-situ absorbent for HCl generated by hydrolyzing organic chlorine and converting into CaCl2(ii) a The quick absorption of HCl generated by the hydrolysis of the organic chloride reduces the inhibition of HCl to the reaction process and the HCl concentration, the catalytic combustion also reduces the concentration of chlorine-free organic matters as byproducts, and the synergistic effect of the two is an important factor for realizing the efficient conversion and removal of the organic chloride. Contains most of calcium sulfate asThe fibrous calcium sulfate has the advantages that the size of other components such as calcium carbonate microparticles is far lower than the length of fibrous calcium sulfate, the fibrous calcium sulfate is used as a binding agent and a reinforcing agent, the treating agent has large inner pore volume, and the treating agent is not easy to expand and pulverize. CaCO contained in the treating agent3The direct contribution to the organochlorine hydrolysis is much lower than that of calcium oxide or calcium hydroxide, so that the organochlorine hydrolysis capacity of the treatment agent is more dependent on Fe2O3、MnO、TiO2But avoids the problems of the prior dechlorinating agent that the dechlorinating agent has low organic chlorine conversion capability and low dechlorinating capacity caused by the conversion of calcium oxide into non-alkaline calcium carbonate when the dechlorinating agent is stored for a long time or the waste gas contains carbon dioxide when calcium oxide or calcium hydroxide is used as the main hydrolysis component of organic chlorine.
In the using process of the treating agent, the temperature of a treating agent bed layer is controlled not to exceed 360 ℃ so as to avoid the reduction of the surface area and the activity of titanium dioxide; the temperature of the treating agent bed layer is determined by the inlet temperature of the waste gas and the content of organic matters in the waste gas, including organic chlorine and chlorine-free organic matters, wherein the chlorine-free organic matters can be generally removed by combustion; the exhaust gas should contain a suitable content of oxygen, for example above 5% by volume, and water vapour, for example 3-5% by volume.
The treating agent for the waste gas containing the organic chloride can be used for purifying the waste gas containing the organic chloride, such as chlorine-containing alkane and chlorine-containing aromatic hydrocarbon. Under the waste gas treatment conditions, the treatment agent of the invention has a penetration dechlorination capacity of more than 10 percent and even more than 15 percent of the mass of the used pretreatment agent, and a saturated dechlorination capacity of more than 15 percent and even more than 20 percent, wherein the penetration is defined as that the organochlorine conversion rate is reduced to less than 90 percent or exceeds the emission limit value of a specific organochlorine substance, and the saturation is defined as that the organochlorine conversion rate is reduced to less than 50 percent or exceeds 5 times of the emission limit value of the specific organochlorine substance; generally does not generate organic chlorine with higher chlorine or increase the complexity of the organic chlorine, does not generate highly toxic chlorine-containing organic matters such as dioxin, and other non-methane hydrocarbon can be lower than 25mg/m3The benzene series organic matter can be less than 10mg/m3。
The treating agent containing organochlorine waste gas is prepared through closing the gas inlet and outlet valve before discharging the agent, cleaning organochlorine and other organic matters in the treating agent bed layer and container, and blowing with air for 0.5-1 hr.
Detailed Description
The technical solution of the present invention will be specifically described and illustrated with reference to the following examples, but the present invention is not limited thereto.
In the following examples and comparative examples, metatitanic acid powder with a mean particle size of 0.72 μm was used, sulfuric acid with a sulfur content of 4.0m% and titanium dioxide of 80m% were produced at 1150 ℃; the average grain diameter of the light calcium carbonate powder is 2 mu m, and the specific surface area is 5m2Per gram, purity 99.5%; ferrous sulfate is a byproduct of titanium dioxide device in sulfuric acid method and contains FeSO47H2O 90.1%、MnSO40.7%、TiOSO40.5 percent; manganese sulfate containing MnSO4H2O99%。
Example 1
The treating agent is prepared according to the following steps:
A. adding 90kg of water into a reaction kettle, adding 25kg of ferrous sulfate and 10kg of manganese sulfate, heating to 50 ℃, stirring for dissolving, adding 12kg of metatitanic acid during stirring, pulping, gradually adding light calcium carbonate powder for reaction, heating to 85 ℃, using pH3.5 as a feeding reaction control end point of the superfine heavy calcium carbonate powder, maintaining the reaction temperature for aging for 3hr, and obtaining slurry containing calcium sulfate fibers, wherein the pH is 3.5-3.7 after the aging process is completed;
B. putting the rest light calcium carbonate powder (75 kg together with the step A) into a kneader, adding 1.5kg of sesbania powder, uniformly mixing, gradually spraying the slurry containing the calcium sulfate fibers, kneading, and extruding into strips with the outer diameter of 3mm in a strip extruding machine;
C. drying the extruded strip at 120 deg.C for 5hr, and baking 2kg of the dried strip at 430 deg.C in air for 3hr to obtain the final product.
Example 2
2kg of the dried noodle obtained in step C of example 1 was calcined at 420 ℃ under air for 4hr to obtain a treating agent.
Example 3
The remaining dried strands from step C of example 1 were calcined in an industrial furnace at 450 ℃ under air conditions for 2.5hr to produce a treating agent.
Comparative example 1
The treatment was prepared essentially as in example 1, except that manganese sulfate was not used.
Comparative example 2
A treatment was prepared essentially as in example 1 except that ferrous sulfate was not used.
Comparative example 3
A treating agent was prepared substantially as in example 1 except that metatitanic acid was not used.
Comparative example 4
A treating agent was prepared substantially as in example 1 except that the aging treatment was not conducted in step A.
The treating agents prepared in the above examples 1-3 and comparative examples 1-3 all had a side pressure strength of more than 70N/cm and a pore volume of more than 0.30 ml/g; the treating agent prepared in comparative example 4 had a side pressure strength of 56N/cm and a pore volume of 0.21 ml/g.
Evaluation examples
The treating agents prepared in examples 1 to 3 and comparative examples 1 to 3 were each tested in a small evaluation apparatus, and each contained 60ml of the agent; the gas conditions in the first stage of 50hr each are 700mg/m dichloroethane3About (containing 500mg/m chlorine in turn)3) 5% by volume of oxygen and 3.5-4% by volume of water vapor, the balance being nitrogen; the gas condition for the second stage of 50hr was 620mg/m of p-dichlorobenzene3About (containing 300mg/m of chlorine in total)3) 5% by volume of oxygen, 2% by volume of carbon dioxide and 3.5-4% by volume of water vapor, the balance being nitrogen; the gas space velocity is 500hr-1The bed temperature was 330 ℃.
The evaluation results included: the treatment agents of examples 1-3 all had vent gases with dichloroethane contents of less than 10mg/m for 50hr of treatment time in each of the first stages3The total amount of organic chlorine is less than 20mg/m3Without generating organic matter of trichloro or more, the non-methane hydrocarbon content is less than 20mg/m3Benzene and benzene series organic matters are not generated, and the selectivity of carbon dioxide is higher than 95 percent; comparative examples 1-2 treatment agent having a dichloroethane content in the off-gas of more than 30mg/m3(ii) a Comparative example 3 treatment agent having a dichloroethane content in the off-gas of more than 60mg/m3Generating a small amount ofOrganic matter of trichloro and above, non-methane hydrocarbon content higher than 30mg/m3。
The treatment agents of examples 1-3 all had outlet gases with dichlorobenzene contents of less than 20mg/m for each second stage of 50hr treatment time3The total amount of organic chlorine is less than 30mg/m3The content of trichloro-organic matter is less than 3mg/m3No generation of organic substances with tetrachloro or more and a non-methane hydrocarbon content of less than 20mg/m3The content of benzene and benzene series organic matters is less than 10mg/m3The selectivity of carbon dioxide is higher than 95 percent; comparative examples 1-2 treatment agent having an outlet gas dichlorobenzene content of greater than 30mg/m3(ii) a Comparative example 3 treatment agent having an outlet gas dichlorobenzene content of greater than 60mg/m3A small amount of organic matter of tetrachloro and above is produced.
Example 1 treating agent after completing the 100hr test of the first two stages, the gas conditions of the second stage were continued, with the gas space velocity changed to 1000hr-1The bed temperature was changed to 350 ℃ for evaluation, and the results in the course of continued evaluation were as follows.
The content of dichlorobenzene in 100-200hr outlet gas is lower than 30mg/m3The total amount of organic chlorine is less than 40mg/m3The content of trichloro-organic matter is less than 5mg/m3No generation of organic substances with tetrachloro or more and a non-methane hydrocarbon content of less than 20mg/m3The content of benzene and benzene series organic matters is less than 10mg/m3The selectivity of carbon dioxide is higher than 95%.
The dichlorobenzene content in 200-step 270hr outlet gas is lower than 40mg/m3The total amount of organic chlorine is less than 50mg/m3The content of trichloro-organic matter is less than 5mg/m3No generation of organic substances with tetrachloro or more and a non-methane hydrocarbon content of less than 20mg/m3The content of benzene and benzene series organic matters is less than 10mg/m3The selectivity of carbon dioxide is higher than 95%.
The dichlorobenzene content in the outlet gas of 270-320hr is lower than 60mg/m3The total amount of organic chlorine is less than 70mg/m3The content of trichloro-organic matter is less than 5mg/m3No generation of organic substances with tetrachloro or more and a non-methane hydrocarbon content of less than 20mg/m3The content of benzene and benzene series organic matters is less than 10mg/m3High selectivity of carbon dioxideAt a rate of 90%.
Then the treating agent is discharged, the treating agent is easy to discharge, the particles are not adhered, the surface is not pulverized, the color is uniform, the inorganic carbon is basically, the chlorine content is measured to be 10.3 percent, and the volume of the chlorine penetration dechlorination reaches more than 11 percent of the mass of the used pre-treating agent.
Example 2 the treating agent was subjected to the second stage test conditions after the completion of the first two stage 100hr test, but the carbon dioxide content in the gas was changed to 4% by volume and the evaluation was continued for 10hr, so that the contents of the components in the outlet gas were not substantially changed; changing the water vapor content of the gas to 8% by volume, and continuing to evaluate for 10hr, wherein the dichlorobenzene content and the total organic chlorine content in the outlet gas are increased by 20-30%, and the treatment effect is recovered after the water vapor content is changed to 3.5-4% by volume.
Claims (7)
1. A treatment agent for waste gas containing organic chlorine is prepared from raw materials including, by mass, 60-80 parts of light calcium carbonate, 10-15 parts of ferrous sulfate, 5-10 parts of manganese sulfate and 5-15 parts of metatitanic acid.
2. The process for producing a treating agent for organic chlorine-containing waste gas as claimed in claim 1, comprising the steps of:
A. adding 80-100 parts of water into a reaction kettle, adding all ferrous sulfate and manganese sulfate, stirring and dissolving, adding metatitanic acid, pulping, gradually adding light calcium carbonate for reaction, heating to 80-95 ℃, taking pH3-4 as a feeding reaction control end point of the light calcium carbonate, maintaining the reaction temperature and pH value range, and aging for 2-3 hours to obtain slurry containing calcium sulfate fibers;
B. adding the rest light calcium carbonate into a kneader, adding sesbania powder, uniformly mixing, gradually spraying the slurry containing the calcium sulfate fibers, kneading, and extruding strips;
C. drying the extruded strip, and calcining at 420-450 deg.C in air for 2-4hr to obtain the final product.
3. The method of claim 2, wherein the metatitanic acid is an intermediate material in the production of titanium dioxide by sulfuric acid process.
4. The method for preparing the organic chloride-containing waste gas treating agent according to claim 2, wherein the ferrous sulfate Russian sulfuric acid process titanium dioxide apparatus produces ferrous sulfate heptahydrate as a byproduct.
5. The method for producing the organic chlorine-containing waste gas treating agent according to claim 2, wherein the light calcium carbonate has an average particle diameter of 1 to 3 μm and a specific surface area of 3 to 6m2/g。
6. The method as claimed in claim 1, wherein the operation conditions are 300-350 ℃ and gas space velocity 100-1000hr-1The waste gas contains more than 5% of oxygen and 3-5% of water vapor by volume.
7. The method of claim 1, wherein the organic chloride comprises chlorinated alkane and chlorinated arene.
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| DE69121550D1 (en) * | 1990-09-06 | 1996-09-26 | Masakatsu Hiraoka | METHOD FOR REMOVING ORGANIC CHLORINATED COMPOUNDS FROM COMBUSTION EXHAUST GASES |
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| CN109126847A (en) * | 2018-08-04 | 2019-01-04 | 山东迅达化工集团有限公司 | The preparation method of the compound catalyst for recovering sulfur of iron oxide titanium dioxide |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE69121550D1 (en) * | 1990-09-06 | 1996-09-26 | Masakatsu Hiraoka | METHOD FOR REMOVING ORGANIC CHLORINATED COMPOUNDS FROM COMBUSTION EXHAUST GASES |
| JP2000157837A (en) * | 1998-11-25 | 2000-06-13 | Kanto Denka Kogyo Co Ltd | Treating agent for halogenating gas, its manufacture and method for making harmless using the same |
| CN109126847A (en) * | 2018-08-04 | 2019-01-04 | 山东迅达化工集团有限公司 | The preparation method of the compound catalyst for recovering sulfur of iron oxide titanium dioxide |
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| XIAODONG MA等: "Catalytic oxidation of 1,2-dichlorobenzene over CaCO3/α-Fe2O3 nanocomposite catalysts", 《APPLIED CATALYSIS A: GENERAL》 * |
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