CN107202333A - A kind of sulfur-bearing VOC method for innocent treatment - Google Patents
A kind of sulfur-bearing VOC method for innocent treatment Download PDFInfo
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- CN107202333A CN107202333A CN201710451220.XA CN201710451220A CN107202333A CN 107202333 A CN107202333 A CN 107202333A CN 201710451220 A CN201710451220 A CN 201710451220A CN 107202333 A CN107202333 A CN 107202333A
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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
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- 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
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Abstract
The invention belongs to the field of environmental protection, a kind of sulfur-bearing VOC method for innocent treatment is disclosed.Methods described is：(1) catalyst is placed in the combustion furnace of sulfur-bearing VOC burning processing devices, is passed through sulfur-bearing VOC gases and combustion-supporting gas；(2) mixed sulfur-bearing VOC gases and combustion-supporting gas carry out catalysis burning in the presence of the catalyst of catalytic combustion burner, and the gas of gained is finally absorbed by alkaline matter after burning；Catalyst described in step (1) is major catalyst, major catalyst and co-catalyst, major catalyst and carrier or major catalyst, co-catalyst and carrier.The method of the present invention is simple, efficiently, used catalyst can increase the local concentration of sulfur-bearing VOC gases and combustion-supporting gas, also its chemical bond energy can be weakened, increase its reactivity, make sulfur-bearing VOC catalysis burn to be easier to make for, react more thorough, effectively realize sulfur-bearing VOC harmless processing.
Description
Technical field
The invention belongs to field of environment protection, the catalysis burning nothing of more particularly to a kind of sulfur-bearing volatile organic matter (VOC)
Evilization processing method.
Background technology
Waste tire, medical waste, house refuse, oily waste, general industry discarded object, discarded agricultural chemicals and its raw material
Deng generally can all have sulfur-containing compound in poisonous waste, either take Pintsch process to handle waste tire, still adopt
With burning method harmless treatment waste tire, medical waste, house refuse, oily waste, general industry discarded object, discarded agriculture
The poisonous waste such as medicine and its raw material, can all produce sulfur-bearing volatile organic matter (VOC).
At present, VOC method for innocent treatment mainly has two classes.One class is absorption method；Another kind of is catalysis burning.
The advantage of absorption method is that equipment is simple, with low content of technology, small investment, but the operating cost of this method is high.This method
It is the air purification method that VOC in air is optionally adsorbed using porous solid adsorbent surface.In molecular attraction or change
Learn in the presence of bonding force, VOC is attracted to adsorbent surface, so as to reach the purpose of separation.When adsorbent surface is covered with VOC,
When reaching adsorption saturation, adsorbent is to lose adsorption capacity.Now need to take appropriate regeneration, will adsorb on surface
VOC desorptions, adsorbent is possessed adsorption capacity again.Simultaneously the VOC of desorption is transferred to appropriate position to enter
The processing of one step.
Compared to absorption method, VOC catalysis burning is a kind of thoroughly method for innocent treatment, in the absence of turning for pollutant
Move, VOC can be completely converted into carbon dioxide (CO2), water (H2) and sulfur dioxide (SO O2).Wherein CO2、H2O environmental sounds,
Sour gas SO2It is easy to by calcium carbonate (CaCO3), calcium oxide (CaO), calcium hydroxide (Ca (OH)2) etc. alkaline matter absorb remove
To the greatest extent.
For not sulfur-bearing VOC, extremely had as the catalysis burning harmless treatment of catalyst using metal platinum, palladium, ruthenium, rhodium
Effect, completely, thoroughly can change into CO by VOC2And H2O.But for sulfur-bearing VOC, then can not use proves non-in other industry
Often the noble metal such as effective platinum, palladium, ruthenium, rhodium carries out harmless treatment as catalyst.
The content of the invention
For the deficiency of prior art, the present invention proposes the catalysis burning method for innocent treatment of sulfur-bearing VOC a kind of, will
Sulfur-bearing VOC is completely converted into CO2、H2O and SO2.Wherein CO2、H2O environmental sounds, sour gas SO2It is easy to by calcium carbonate
(CaCO3), calcium oxide (CaO), calcium hydroxide (Ca (OH)2) etc. cheap alkaline matter easily absorb and eliminate, sulfur-bearing VOC without
The concentration and mass rate of emission of each remaining component can reach discharging standards in tail gas after evilization processing.Adjustment catalysis burning
Technological parameter (catalysis bed length or gas VOC flow into the linear velocity of catalytic bed), can make tail gas after sulfur-bearing VOC harmless treatments
In each remaining component concentration and mass rate of emission can reach the tightened up discharge standard of following country.
The purpose of the present invention is achieved through the following technical solutions：
The catalysis burning method for innocent treatment of sulfur-bearing VOC a kind of, comprises the following steps：
(1) catalyst is placed in the combustion furnace of sulfur-bearing VOC burning processing devices, is passed through sulfur-bearing VOC gases and combustion-supporting gas
Body；
(2) mixed sulfur-bearing VOC gases and combustion-supporting gas carry out catalysis combustion under the catalyst action of catalytic combustion burner
Burn, the gas of gained is finally absorbed by alkaline matter after burning.
Sulfur-bearing VOC burning processing devices described in step (1) include setting on the outside of catalytic combustion burner, the catalytic combustion burner
There is zone of heating, the outside of zone of heating is provided with thermal insulation layer；One end of the catalytic combustion burner is provided with reacting gas air inlet, described anti-
Gas inlet is answered to be connected by pipeline with sulfur-bearing VOC air accumulators and oxygen/air air accumulator, the pipeline is that two-way gas enters
Tracheae, i.e. sulfur-bearing VOC air inlet pipe and oxygen/air air inlet pipe, per the connection digital display mass flowmenter of air inlet pipe all the way and regulating valve
Door, is provided with pump between the control valve and air accumulator；The other end of the catalytic combustion burner is provided with gas outlet.
The sulfur-bearing VOC burning processing devices also include gas mixer and heat-exchanger rig, the gas mixer
Provided with air inlet and gas outlet, air inlet is connected by pipeline with sulfur-bearing VOC air accumulators and oxygen/air air accumulator, gas outlet
It is connected with reacting gas air inlet by pipeline；The gas mixer through heat-exchanger rig, one end of heat-exchanger rig with
The gas outlet connection of catalytic combustion burner, the other end is connected with the device equipped with alkaline matter.The heat-exchanger rig is utilized more than tail gas
Heat preheating pending sulfur-bearing VOC gases and combustion-supporting gas, to save the energy, reduce processing cost.
The outer wall of the catalytic combustion burner is provided with thermocouple, so as to collecting temperature signal.
The mode of heating of the zone of heating can be by the way of combustion gas (including VOC) burning or using electricity
Mode of heating.
Sulfur-bearing VOC (dusty gas) described in step (1) and combustion-supporting gas are introduced with 0.01-1000m/min linear velocity
In catalytic combustion burner；According to the length adjustment linear velocity of combustion furnace so that burning after tail gas in each remaining component concentration it is remote
Less than the concentration of discharging standards.
The temperature that burning is catalyzed described in step (2) is 300-1300 DEG C.
Catalyst described in step (1) is major catalyst, the composite catalyst that major catalyst and co-catalyst are composited,
The composite catalyzing that the composite catalyst or major catalyst, co-catalyst and carrier that major catalyst is composited with carrier are composited
Agent.
The major catalyst is metal, metal oxide or its mixture；The metal be vanadium, chromium, manganese, iron, cobalt, copper,
Gallium, germanium, yttrium, silver, indium, antimony, hafnium, tantalum, tungsten, osmium, iridium, gold, lead, bismuth, americium, cerium, neptunium, plutonium, uranium；
The metal oxide be vanadium, chromium, manganese, iron, cobalt, copper, gallium, germanium, yttrium, silver, indium, antimony, hafnium, tantalum, tungsten, osmium, iridium,
One or more of gold, lead, bismuth, americium, cerium, neptunium, plutonium, oxide of uranium formation, the oxide includes the oxidation of different valence state
Thing.
The particle diameter of the major catalyst is 0.01nm-1000mm.
Co-catalyst described in step (1) be metal, nonmetallic, metal oxide, nonmetal oxide or its mixture,
It is preferably two or more；The metal be lithium, beryllium, sodium, magnesium, aluminium, potassium, calcium, scandium, titanium, zinc, gallium, germanium, rubidium, strontium, yttrium, zirconium, niobium,
More than one in molybdenum, technetium, silver, indium, tin, antimony, caesium, barium, lanthanum, cerium, samarium, lutetium, iridium, gadolinium, tantalum, tungsten, radium, hafnium, uranium, thorium；It is described non-
Metal is more than one in arsenic, silicon, phosphorus, selenium, boron, tellurium；In the oxide that the metal oxide is formed by above-mentioned metal
More than one, the nonmetal oxide is by one or more of above-mentioned nonmetallic oxide formed, the oxide bag
Include the oxide of different valence state.
The co-catalyst is a kind of macrostructure that can significantly improve major catalyst and electronic structure performance, can be improved
The material of the activity of major catalyst, selectivity and stability, such as CeO2Mobility and catalyst storage oxygen with increase Lattice Oxygen
The ability of amount.The particle diameter of the co-catalyst is 0.01-1000mm.
The pore passage structure of molecular sieve can accelerate catalytic reaction with adsorption gas molecule.
Carrier described in step (1) is metal oxide, nonmetal oxide and its mixture, or is metallic element
The material constituted with nonmetalloid；Metal oxide be potassium, sodium, beryllium, calcium, magnesium, aluminium, titanium, zirconium, iron, cobalt, chromium, manganese, copper, gallium,
Zinc, vanadium, the oxide of the different valence state of germanium；Nonmetal oxide is silicon, phosphorus, sulphur, the oxide of the different valence state of boron.
The carrier be powdered with high-ratio surface or suitable pore passage structure or particulate material, or for layer
Shape structure or fibrous material.
The carrier is molecular sieve, kaolin, montmorillonite, kaolinite, galapectite, hydromica, illite and quartz, length
The mineral such as stone, the carrier can also be ceramic honey comb, fiber ceramics.
The carrier is a kind of effective surface area that can significantly improve major catalyst, provides suitable aperture, can be improved
The mechanical strength of major catalyst, improve major catalyst heat endurance, can as major catalyst skeleton or the material of branch lining person.
The catalyst described in the step (1) is mixture and during containing metal oxide, and the catalyst is preferred to use
It is prepared by coprecipitation or ion-exchange or infusion process；
The coprecipitation is to be mixed the aqueous solution containing metal ion, or the aqueous solution containing metal ion
Mixed with metal or metal oxide, using the pH of alkali adjustment solution to alkalescent, metal ion is precipitated, filtering,
Calcining, obtains catalyst.The condition of the calcining is to calcine 10~240min in 300-1300 DEG C.It is described containing metal ion
The aqueous solution is the nitrate solution and/or chloride solution of metal.The alkali is sodium hydroxide solution or ammoniacal liquor.The metal from
Son is the ion corresponding to metal in above-mentioned catalyst, and metal, metal oxide are metal, metal oxidation in above-mentioned catalyst
Thing.
The nitrate of the metal refers to Cu (NO3)2、Cr(NO3)3、Mn(NO3)2、Ir(NO3)3、Fe(NO3)3、Co
(NO3)2、AgNO3Deng the nitrate of transition metal, Al (NO3)3、Ti(NO3)4、Ce(NO3)4Deng nitrate；The chlorination of the metal
Thing solution refers to iron chloride, copper chloride, the chloride such as manganese chloride.
The ion-exchange or infusion process are that the container that will be equipped with the carrier with pore passage structure or lamellar structure is carried out
Vacuumize, then the aqueous solution containing metal ion is added in container, the aqueous solution submergence containing metal ion has duct knot
The carrier of structure or lamellar structure, immersion a period of time, the pH for adjusting solution with alkali is to alkalescent, and filtering after having reacted, calcining is obtained
To catalyst.
The aqueous solution containing metal ion is the nitrate solution and/or chloride solution of metal.The alkali is hydrogen
Sodium hydroxide solution or ammoniacal liquor.The metal ion for metal in above-mentioned catalyst, (with helping urge by the metal of major catalyst, major catalyst
The metal of agent) corresponding to ion, the carrier with pore passage structure or lamellar structure is preferably molecular sieve, kaolin,
Montmorillonite, kaolinite, galapectite, hydromica, illite, quartz, feldspar and ceramic honey comb.
The soak time is 5-360 minutes, and the condition of the calcining is to calcine 10~240min in 300-1300 DEG C.
Combustion-supporting gas described in step (1) is air, oxygen, or other oxidants.
It is empty on the outside of the catalyst surface atom of the present invention, an inside pulling force can be produced.The power can be to gas
Phase molecule produces suction-operated, so that combustion adjuvant O2Molecule and hydrocarbon molecules will be much in the local concentration of catalyst surface
More than its concentration in the gas phase, to increase its reaction rate.
In addition, catalyst can weaken the chemical bond between combustion adjuvant and each atom of VOC intramoleculars, reduction combustion adjuvant with
The activation energy of combustion reaction occurs for VOC, improves the speed of the innoxious eliminations of VOC.
The particle diameter of the catalyst is 0.01-1000mm, is adjusted according to the internal diameter and length of combustion furnace.
The internal diameter 1-50000mm of the combustion furnace, length is 10-100000mm.
Combustion furnace is preferably earthenware in the sulfur-bearing VOC burning processing devices, and the two ends of earthenware are provided with barrier layer, with
Exempt from catalyst outflow, lose, while being respectively equipped with air inlet and gas outlet on the barrier layer of two ends, it is ensured that sulfur-bearing VOC gases and help
Combustion gas physical efficiency is entered in earthenware with certain linear velocity, and the tail gas after burning can flow out earthenware.
Catalytic bed (i.e. combustion furnace) is integral reactor, its total conversion in the sulfur-bearing VOC burning processing devices of the present invention
It is the summation of each small section conversion ratio of catalytic bed, can be separately won by the length product to whole catalytic bed.In order to improve VOC
Conversion ratio, O2It is much excessive, therefore in VOC innocent treatment procedure, O2Concentration is considered as constant.It is assumed that VOC's urges
It is simple first order reaction to change burning, then is understood according to the law of mass action：
In formula：C is that VOC concentration, k are reaction rate constant, and t is the time.It is assumed that C0For VOC initial concentration, v is VOC
Gas linear rate of flow, l is catalysis bed length, then dt=dl/v, substitutes into formula (1), and arrange：
C=C0e-kl/v (2)
From formula (2), catalytic bed is longer, and gas flow rate is lower, and VOC residual concentration is just smaller, therefore, it can pair
The adjustment of catalytic combustion process condition (catalysis bed length, VOC gases linear rate of flow), it is possible to obtain satisfied processing effect
Really.VOC catalyst combustion reactions for not being first order reaction, it can be deduced that similar conclusion, only residual concentration and catalytic bed
Specific mathematic(al) representation between length, gas flow rates is different.
Major catalyst, co-catalyst and carrier used in the catalysis burning are not sent out to be one or more with sulfur-containing compound
Material (such as alundum (Al2O3), Al of raw reaction2O3), although or can be reacted with sulfur-containing compound, generation sulfide
Material (such as di-iron trioxide, Fe that can be reoxidized in catalytic condition2O3), or its arbitrary proportion compound.
Compared with prior art, the present invention has advantages below and beneficial effect：
The method of the present invention is simple, efficiently, has preferable treatment effect to sulfur-bearing VOC, sulfur-bearing VOC can be completely converted into
CO2、H2O and SO2, the concentration for realizing each remaining component in tail gas after sulfur-bearing VOC harmless treatment, harmless treatment is far low
In the concentration of discharging standards.
Brief description of the drawings
Fig. 1 is the structural representation of sulfur-bearing VOC burning processing devices in the present invention, and wherein 1- catalytic combustion burners are ceramics
Pipe, 2- zones of heating, 3- thermal insulation layers, 4- catalyst, 5- barrier layers, 6,7- flowmeters, 8,9- pumps, 10,11,16- pressure gauges, 12-
Sulfur-bearing VOC air accumulators, 13- oxygen/air air accumulators, the tail gas after 14- burnings, 15- sample taps, 17- thermocouples.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
The structural representation of sulfur-bearing VOC burning processing devices is as shown in Figure 1 in the present invention.The sulfur-bearing VOC burnings processing
Device includes catalytic combustion burner 1 (such as：Earthenware, the two ends of earthenware are provided with barrier layer 5), set on the outside of the catalytic combustion burner
There is zone of heating 2, the outside of zone of heating is provided with thermal insulation layer 3；One end of the catalytic combustion burner (on the barrier layer of earthenware one end)
Provided with reacting gas air inlet, the reacting gas air inlet passes through pipeline and sulfur-bearing VOC air accumulators 12 and oxygen/air gas storage
Tank 13 is connected, and the pipeline (pipeline is provided with thermocouple) is two-way gas inlet pipe, i.e. sulfur-bearing VOC air inlet pipe and oxygen/sky
Gas air inlet pipe, per the connection digital display of air inlet pipe all the way mass flowmenter 6,7 and pump 8,9, the pump is close to air accumulator, the pump and stream
Control valve and pressure gauge 10,11 are provided between gauge；The other end (the barrier layer of the earthenware other end of the catalytic combustion burner
On) it is provided with gas outlet.On the pipeline of the gas outlet (i.e. burn after tail gas 14 passage) provided with thermocouple, pressure gauge 16 with
And sample tap 15.
The sulfur-bearing VOC burning processing devices also include gas mixer and heat-exchanger rig, the gas mixer
Provided with air inlet and gas outlet, air inlet is connected by pipeline with sulfur-bearing VOC air accumulators and oxygen/air air accumulator, gas outlet
It is connected with reacting gas air inlet by pipeline；The gas mixer through heat-exchanger rig, one end of heat-exchanger rig with
The gas outlet connection of catalytic combustion burner, the other end is connected with the device equipped with alkaline matter.
The outer wall of the catalytic combustion burner is provided with thermocouple 17.
Embodiment 1
(1) by cuprous oxide (Cu of the particle diameter for 0.1mm2O) powder and the titanium dioxide metallic cerium (CeO that particle diameter is 0.1mm2)
By 8：2 mass ratio is well mixed, and is loaded into internal diameter as shown in Figure 1 for 50mm, in a length of 800mm earthenware, earthenware
Two ends are provided with barrier layer, and barrier layer is respectively equipped with gas outlet and air inlet；
(2) by sulfur-bearing VOC gases (composition as shown in table 1) and combustion-supporting gas oxygen with 1.2m/min linear velocity by entering
Gas port enters in earthenware, and 680 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail
The VOC each component contents remained in gas are below national discharge standard of air pollutants, as shown in table 1.
VOC harmless treatment result in the embodiment 1 of table 1
* the former Soviet Union；East Germany before *
Embodiment 2
(1) by particle diameter is 0.1mm cupric oxide (CuO) powder and particle diameter is 0.1mm alundum (Al2O3) (Al2O3) press 6：4
Mass ratio is well mixed, and is loaded into internal diameter as shown in Figure 1 for 50mm, in a length of 800mm earthenware, earthenware two ends are provided with
Barrier layer, barrier layer is respectively equipped with gas outlet and air inlet；
(2) by sulfur-bearing VOC gases (composition as shown in table 2) and combustion-supporting gas oxygen with 1.2m/min linear velocity by entering
Gas port enters in earthenware, and 720 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail
The VOC each component contents remained in gas are below national discharge standard of air pollutants, as shown in table 2.
VOC harmless treatment result in the embodiment 2 of table 2
* the former Soviet Union；East Germany before *
Embodiment 3
(1) by particle diameter is 0.1mm copper powders and particle diameter is 0.1mm titanium dioxide Titanium (TiO2) press 7：3 mass ratio is mixed
Close uniform, be loaded into internal diameter as shown in Figure 1 for 50mm, in a length of 800mm earthenware, earthenware two ends are provided with barrier layer,
Two ends barrier layer is respectively equipped with gas outlet and air inlet；
(2) by sulfur-bearing VOC gases (composition as shown in table 1) and combustion-supporting gas oxygen with 1.2m/min linear velocity by entering
Gas port enters in earthenware, and 720 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail
The VOC each component contents remained in gas are below national discharge standard of air pollutants, as shown in table 3.
VOC harmless treatment result in the embodiment 3 of table 3
* the former Soviet Union；East Germany before *
Embodiment 4
(1) it is 0.1mm di-iron trioxides (Fe by particle diameter2O3) powder and particle diameter be 0.1mm titanium dioxide metallic cerium (CeO2)
By 6：4 mass ratio is well mixed, and is loaded into internal diameter as shown in Figure 1 for 50mm, in a length of 800mm earthenware, ceramics
Pipe two ends are provided with barrier layer, and two ends barrier layer is respectively equipped with gas outlet and air inlet；
(2) by sulfur-bearing VOC gases (composition as shown in table 1) and combustion-supporting gas oxygen with 1.2m/min linear velocity by entering
Gas port enters in earthenware, and 720 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail
The VOC each component contents remained in gas are below national discharge standard of air pollutants, as shown in table 4.
VOC harmless treatment result in the embodiment 4 of table 4
* the former Soviet Union；East Germany before *
Embodiment 5
By the titanium dioxide metallic cerium (CeO that particle diameter is 0.1mm iron powders and particle diameter is 0.1mm2) press 6：4 mass ratio mixing is equal
It is even, internal diameter as shown in Figure 1 is loaded into for 50mm, and in a length of 800mm earthenware, earthenware two ends are provided with barrier layer, two ends
Barrier layer is respectively equipped with gas outlet and air inlet；
(2) by sulfur-bearing VOC gases (composition as shown in table 1) and combustion-supporting gas oxygen with 1.2m/min linear velocity by entering
Gas port enters in earthenware, and 720 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail
The VOC each component contents remained in gas are below national discharge standard of air pollutants, as shown in table 5.
VOC harmless treatment result in the embodiment 5 of table 5
* the former Soviet Union；East Germany before *
Embodiment 6
(1) by particle diameter is the stainless steel powders of 0.1mm 304 and particle diameter is 0.1mm titanium dioxide metallic cerium (CeO2) press 6：4
Mass ratio is well mixed, and is loaded into internal diameter as shown in Figure 1 for 50mm, in a length of 800mm earthenware, earthenware two ends are provided with
Barrier layer, barrier layer is respectively equipped with gas outlet and air inlet；
(2) by sulfur-bearing VOC gases (composition as shown in table 1) and combustion-supporting gas oxygen with 1.2m/min linear velocity by entering
Gas port enters in earthenware, and 720 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail
The VOC each component contents remained in gas are below national discharge standard of air pollutants, as shown in table 6.
VOC harmless treatment result in the embodiment 6 of table 6
| Sequence number | Pollutant | Allow concentration of emission (mg/m3) | Concentration (mg/m after processing3) |
| 1 | Ethyl mercaptan | 1* | ≦0.05 |
| 2 | Thiophene | 0.2** | ≦0.02 |
| 3 | Benzene | 17 | ≦0.50 |
| 4 | Dimethylbenzene | 90 | ≦1.5 |
| 5 | Phenols | 115 | ≦0.10 |
| 6 | Formaldehyde | 30 | ≦0.25 |
| 7 | Acrylonitrile | 26 | ≦0.75 |
| 8 | Methanol | 220 | ≦15 |
| 9 | Phenyl amines | 25 | ≦0.50 |
| 10 | Nitrobenzene | 20 | ≦0.01 |
| 11 | NMHC | 150 | ≦4.0 |
* the former Soviet Union；East Germany before *
Embodiment 7
(1) by particle diameter is 0.1mm ferric oxide powders and particle diameter is 0.1mm copper powder by 6：4 mass ratio is mixed
Close uniform, be loaded into internal diameter as shown in Figure 1 for 50mm, in a length of 800mm earthenware, earthenware two ends are provided with barrier layer,
Barrier layer is respectively equipped with gas outlet and air inlet；
(2) by sulfur-bearing VOC gases (composition as shown in table 1) and combustion-supporting gas oxygen with 1.2m/min linear velocity by entering
Gas port enters in earthenware, and 720 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail
The VOC each component contents remained in gas are below national discharge standard of air pollutants, as shown in table 7.
VOC harmless treatment result in the embodiment 7 of table 7
| Sequence number | Pollutant | Allow concentration of emission (mg/m3) | Concentration (mg/m after processing3) |
| 1 | Ethyl mercaptan | 1* | ≦0.05 |
| 2 | Thiophene | 0.2** | ≦0.02 |
| 3 | Benzene | 17 | ≦0.50 |
| 4 | Dimethylbenzene | 90 | ≦1.5 |
| 5 | Phenols | 115 | ≦0.10 |
| 6 | Formaldehyde | 30 | ≦0.25 |
| 7 | Acrylonitrile | 26 | ≦0.75 |
| 8 | Methanol | 220 | ≦15 |
| 9 | Phenyl amines | 25 | ≦0.50 |
| 10 | Nitrobenzene | 20 | ≦0.01 |
| 11 | NMHC | 150 | ≦4.0 |
* the former Soviet Union；East Germany before *
Embodiment 8
(1) by particle diameter is 0.1mm iron powders and particle diameter is 0.1mm copper powder by 7：3 mass ratio is well mixed, filling
It is that in 50mm, a length of 800mm earthenware, earthenware two ends are provided with barrier layer to internal diameter as shown in Figure 1, barrier layer is set respectively
There are gas outlet and air inlet；
(2) by sulfur-bearing VOC gases (composition as shown in table 1) and combustion-supporting gas oxygen with 1.2m/min linear velocity by entering
Gas port enters in earthenware, and 720 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail
The VOC each component contents remained in gas are below national discharge standard of air pollutants, as shown in table 8.
VOC harmless treatment result in the embodiment 8 of table 8
* the former Soviet Union；East Germany before *
Embodiment 9
(1) by titanium dioxide metallic cerium (CeO of the 50kg particle diameters for 0.1mm2) it is put into 0.4m3Iron chloride (FeCl3) saturation is molten
In liquid, in the case where being stirred continuously, 1wt% sodium hydroxide (NaOH) solution is slowly added into iron chloride saturated solution to iron chloride
The pH of solution is 8.5, stirring a period of time, filtering, drying composite catalyst；
Composite catalyst is loaded into internal diameter as shown in Figure 1 for 50mm, in a length of 800mm earthenware, earthenware two
End is provided with barrier layer, and barrier layer is respectively equipped with gas outlet and air inlet；
(2) by sulfur-bearing VOC gases (composition as shown in table 1) and combustion-supporting gas oxygen with 1.2m/min linear velocity by entering
Gas port enters in earthenware, and 680 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail
The VOC each component contents remained in gas are below national discharge standard of air pollutants, as shown in table 9.
VOC harmless treatment result in the embodiment 9 of table 9
* the former Soviet Union；East Germany before *
Embodiment 10
(1) by titanium dioxide metallic cerium (CeO of the 50kg particle diameters for 0.1mm2) it is put into 0.4m3Copper chloride (CuCl2) saturation is molten
In liquid, in the case where being stirred continuously, 1wt% sodium hydroxide (NaOH) solution is slowly added into copper chloride saturated solution to copper chloride
The pH of solution is 8.5, is stirred, filtering, drying composite catalyst；
Composite catalyst is loaded into internal diameter as shown in Figure 1 for 50mm, in a length of 800mm earthenware, earthenware two
End is provided with barrier layer, and barrier layer is respectively equipped with gas outlet and air inlet；
(2) by sulfur-bearing VOC gases (composition as shown in table 1) and combustion-supporting gas oxygen with 1.2m/min linear velocity by entering
Gas port enters in earthenware, and 680 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail
The VOC each component contents remained in gas are below national discharge standard of air pollutants, as shown in table 10.
VOC harmless treatment result in the embodiment 10 of table 10
| Sequence number | Pollutant | Allow concentration of emission (mg/m3) | Concentration (mg/m after processing3) |
| 1 | Ethyl mercaptan | 1* | ≦0.03 |
| 2 | Thiophene | 0.2** | ≦0.06 |
| 3 | Benzene | 17 | ≦0.2 |
| 4 | Dimethylbenzene | 90 | ≦1.0 |
| 5 | Phenols | 115 | ≦0.09 |
| 6 | Formaldehyde | 30 | ≦0.22 |
| 7 | Acrylonitrile | 26 | ≦0.65 |
| 8 | Methanol | 220 | ≦4 |
| 9 | Phenyl amines | 25 | ≦0.30 |
| 10 | Nitrobenzene | 20 | ≦0.020 |
| 11 | NMHC | 150 | ≦4.0 |
* the former Soviet Union；East Germany before *
Embodiment 11
(1) concentration is mixed for 2mol/L 2000L cerous nitrate solutions with 1.5mol/L 2000L copper nitrate solutions
It is even, in the case where being stirred continuously, 1wt% sodium hydroxide solution is slowly added into mixed solution to the pH value 7.5 of mixed solution, is stirred
Mix, filter, calcining produces composite catalyst in 3 hours in 1100 DEG C；
Composite catalyst is loaded into internal diameter as shown in Figure 1 for 50mm, in a length of 800mm earthenware, earthenware two
End is provided with barrier layer, and barrier layer is respectively equipped with gas outlet and air inlet；
(2) by sulfur-bearing VOC gases (composition as shown in table 1) and combustion-supporting gas oxygen with 1.2m/min linear velocity by entering
Gas port enters in earthenware, and 680 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail
The VOC each component contents remained in gas are below national discharge standard of air pollutants, as shown in table 11.
VOC harmless treatment result in the embodiment 10 of table 11
| Sequence number | Pollutant | Allow concentration of emission (mg/m3) | Concentration (mg/m after processing3) |
| 1 | Ethyl mercaptan | 1* | ≦0.04 |
| 2 | Thiophene | 0.2** | ≦0.02 |
| 3 | Benzene | 17 | ≦0.6 |
| 4 | Dimethylbenzene | 90 | ≦0.2 |
| 5 | Phenols | 115 | ≦0.13 |
| 6 | Formaldehyde | 30 | ≦0.2 |
| 7 | Acrylonitrile | 26 | ≦0.65 |
| 8 | Methanol | 220 | ≦4.1 |
| 9 | Phenyl amines | 25 | ≦0.30 |
| 10 | Nitrobenzene | 20 | ≦0.20 |
| 11 | NMHC | 150 | ≦3.0 |
* the former Soviet Union；East Germany before *
Embodiment 12
(1) 50kg calcium Y type molecular sieves are placed in 200L vacuum kettle, vacuumize until kettle in air pressure be less than 10Pa,
To remove the air inside molecular sieve pores, using vacuum by 1mol/L Cu (NO3)2Until completely in solution suction vacuum kettle
Calcium Y type molecular sieve is flooded, the pH value that immersion adjusts solution after 10 minutes with ammoniacal liquor is 7.5, then filtering, finally by after filtering
Molecular sieve is calcined 180 minutes in 880 DEG C of high temperature, that is, obtains porous composite catalyst；
Porous composite catalyst is loaded into internal diameter as shown in Figure 1 for 50mm, in a length of 800mm earthenware, pottery
Porcelain tube two ends are provided with barrier layer, and barrier layer is respectively equipped with gas outlet and air inlet；
(2) sulfur-bearing VOC gases (composition is as shown in table 1) and combustion-supporting gas can be passed through into air inlet with 1.2m/min linear velocity
Mouth enters in earthenware, and 680 DEG C of catalysis burnings, the tail gas after burning flows out from gas outlet, finally absorbed by alkaline matter.Tail gas
The VOC each component contents of middle residual are below national discharge standard of air pollutants, as shown in table 12.
VOC harmless treatment result in the embodiment 10 of table 12
| Sequence number | Pollutant | Allow concentration of emission (mg/m3) | Concentration (mg/m after processing3) |
| 1 | Ethyl mercaptan | 1* | ≦0.04 |
| 2 | Thiophene | 0.2** | ≦0.02 |
| 3 | Benzene | 17 | ≦0.6 |
| 4 | Dimethylbenzene | 90 | ≦0.2 |
| 5 | Phenols | 115 | ≦0.13 |
| 6 | Formaldehyde | 30 | ≦0.2 |
| 7 | Acrylonitrile | 26 | ≦0.65 |
| 8 | Methanol | 220 | ≦4.1 |
| 9 | Phenyl amines | 25 | ≦0.30 |
| 10 | Nitrobenzene | 20 | ≦0.20 |
| 11 | NMHC | 150 | ≦3.0 |
* the former Soviet Union；East Germany before *.
Claims (9)
1. the catalysis burning method for innocent treatment of sulfur-bearing VOC a kind of, it is characterised in that：Comprise the following steps：
(1) catalyst is placed in the combustion furnace of sulfur-bearing VOC burning processing devices, is passed through sulfur-bearing VOC gases and combustion-supporting gas；
(2) mixed sulfur-bearing VOC gases and combustion-supporting gas carry out catalysis burning under the catalyst action of catalytic combustion burner, combustion
The gas of gained is finally absorbed by alkaline matter after burning；
Catalyst described in step (1) is major catalyst, and the composite catalyst that major catalyst is composited with co-catalyst is sponsored
The composite catalyst that the composite catalyst or major catalyst, co-catalyst and carrier that agent is composited with carrier are composited；
The major catalyst is metal, metal oxide or its mixture；The metal be vanadium, chromium, manganese, iron, cobalt, copper, gallium,
Germanium, yttrium, silver, indium, antimony, hafnium, tantalum, tungsten, osmium, iridium, gold, lead, bismuth, americium, cerium, neptunium, plutonium, uranium；
The metal oxide be vanadium, chromium, manganese, iron, cobalt, copper, gallium, germanium, yttrium, silver, indium, antimony, hafnium, tantalum, tungsten, osmium, iridium, gold, lead,
One or more of bismuth, americium, cerium, neptunium, plutonium, oxide of uranium formation, the oxide includes the oxide of different valence state.
2. according to claim 1 sulfur-bearing VOC catalysis burning method for innocent treatment, it is characterised in that：Institute in step (1)
Co-catalyst is stated for metal, nonmetallic, metal oxide, nonmetal oxide or its mixture；The metal be lithium, beryllium, sodium,
Magnesium, aluminium, potassium, calcium, scandium, titanium, zinc, gallium, germanium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, silver, indium, tin, antimony, caesium, barium, lanthanum, cerium, samarium,
More than one in lutetium, iridium, gadolinium, tantalum, tungsten, radium, hafnium, uranium, thorium；It is described nonmetallic for more than one in arsenic, silicon, phosphorus, selenium, boron, tellurium；
One or more of oxide that the metal oxide is formed by above-mentioned metal, the nonmetal oxide is above-mentioned non-gold
One or more of formed oxide of category, the oxide includes the oxide of different valence state.
3. according to claim 1 sulfur-bearing VOC catalysis burning method for innocent treatment, it is characterised in that：Institute in step (1)
Stating sulfur-bearing VOC burning processing devices includes catalytic combustion burner, and the outside of the catalytic combustion burner is provided with outside zone of heating, zone of heating
Side is provided with thermal insulation layer；One end of the catalytic combustion burner is provided with reacting gas air inlet, and the reacting gas air inlet passes through pipe
Road is connected with sulfur-bearing VOC air accumulators and oxygen/air air accumulator, and the pipeline is two-way gas inlet pipe, i.e. sulfur-bearing VOC air inlets
Pipe and oxygen/air air inlet pipe, per the connection digital display mass flowmenter of air inlet pipe all the way and pump；The other end of the catalytic combustion burner
Provided with gas outlet.
4. according to claim 3 sulfur-bearing VOC catalysis burning method for innocent treatment, it is characterised in that：The sulfur-bearing VOC
Burning processing device also includes gas mixer and heat-exchanger rig, and the gas mixer is provided with air inlet and gas outlet,
Air inlet is connected by pipeline with sulfur-bearing VOC air accumulators and oxygen/air air accumulator, and gas outlet passes through with reacting gas air inlet
Pipeline is connected；The gas mixer connects through heat-exchanger rig, one end of heat-exchanger rig and the gas outlet of catalytic combustion burner
Connect, the other end is connected with the device equipped with alkaline matter；
The outer wall of the catalytic combustion burner is provided with thermocouple.
5. according to claim 1 sulfur-bearing VOC catalysis burning method for innocent treatment, it is characterised in that：Institute in step (1)
Sulfur-bearing VOC and combustion-supporting gas is stated to be introduced into catalytic combustion burner with 0.01-1000m/min linear velocity；Linear velocity is according to combustion furnace
Length be adjusted, according to the length adjustment linear velocity of combustion furnace so that burning after tail gas in each remaining component concentration
Far below the concentration of discharging standards；
The temperature that burning is catalyzed described in step (2) is 300-1300 DEG C.
6. according to claim 1 sulfur-bearing VOC catalysis burning method for innocent treatment, it is characterised in that：Institute in step (1)
Carrier is stated for metal oxide, nonmetal oxide and its mixture, or is that metallic element is constituted with nonmetalloid
Material；Metal oxide is potassium, sodium, beryllium, calcium, magnesium, aluminium, titanium, zirconium, iron, cobalt, chromium, manganese, copper, gallium, zinc, vanadium, the different valence state of germanium
Oxide；Nonmetal oxide is silicon, phosphorus, sulphur, the oxide of the different valence state of boron.
7. according to claim 1 sulfur-bearing VOC catalysis burning method for innocent treatment, it is characterised in that：The carrier is
Powdered with high-ratio surface or pore passage structure or particulate material, or for layer structure or fibrous material.
8. according to claim 7 sulfur-bearing VOC catalysis burning method for innocent treatment, it is characterised in that：The carrier is
Molecular sieve, kaolin, montmorillonite, kaolinite, galapectite, hydromica, illite and quartz, feldspar, ceramic honey comb, fiber pottery
Porcelain.
9. according to claim 1 sulfur-bearing VOC catalysis burning method for innocent treatment, it is characterised in that：When in step (1)
The catalyst be mixture and containing metal oxide when, the catalyst use coprecipitation or ion-exchange or leaching
It is prepared by stain method.
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