CN106377997A - Preparation of harmful gas purifying agent in air flow, and purification method and device by using purifying agent - Google Patents
Preparation of harmful gas purifying agent in air flow, and purification method and device by using purifying agent Download PDFInfo
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- CN106377997A CN106377997A CN201610906058.1A CN201610906058A CN106377997A CN 106377997 A CN106377997 A CN 106377997A CN 201610906058 A CN201610906058 A CN 201610906058A CN 106377997 A CN106377997 A CN 106377997A
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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Abstract
The invention discloses preparation of a harmful gas purifying agent in air flow, and a purification method and device by using the purifying agent. The purifying agent is used for removing oxynitrides, sulfur dioxide, carbon monoxide, VOCs (volatile organic compounds) and other harmful substances from the air flow, and belongs to the technical fields of air pollution control and environmental protection. The preparation method is characterized by comprising the following steps: proportionally mixing ferrous chloride, calcium oxide (or magnesium oxide, or calcium hydroxide or magnesium hydroxide) and other materials according to the procedure, reacting, and carrying out thermal dehydration to obtain a solid mixed compound or complex which is the purifying agent. After the purifying agent is introduced into a gas-solid reaction cylinder, the harmful substances in the air flow are subjected to gas-solid chemical reaction with the purifying agent at a certain temperature so as to be removed. Thus, the purifying agent is simple to operate, and has the characteristics of high treatment efficiency, high treatment capacity and low operating cost. The invention also discloses a related purification device.
Description
Technical field
The present invention relates to the preparation of purifying agent for harmful gases and purification method and device in a kind of air-flow, particularly to from gas
Remove the nuisances such as nitrogen oxides, sulfur dioxide, carbon monoxide and VOCs (hydrocarbon-containiproducts) in stream, belong to atmosphere pollution control
System and environmental protection technical field.
Background technology
Sulfur dioxide (the SO that mankind's activity produces2) and nitrogen oxides (NOx, predominantly NO and NO2) pernicious gas, by firing
What material burning produced accounts for more than 90%.Sulfur dioxide and nitrogen oxides have intoxicating to act on to people and biology, are to cause atmospheric acid
The main cause of rain.China Environmental State Bulletin statistics shows that the Acid Rain Pollution property of China urban has started to by sulphur
Acid type is to ever-increasing compound conversion (the national environmental protection portion of nitrate ion:China Environmental State Bulletin in 2010).In recent years
Come, country newly formulated some new laws and regulations, to the fuel combustion process such as particularly thermoelectricity discharge sulfur dioxide and nitrogen
The pollutants such as oxide have been made stricter control and have been reduced discharging regulation.
The nuisances such as the nitrogen oxides of motor vehicle exhaust emission, sulfur dioxide, carbon monoxide and VOCs (hydrocarbon-containiproducts)
Matter is the main reason of some urban atmosphere hazes.Get more and more with automobile reserved, the atmosphere polluting problem thus causing
Increasingly severe, the pollution of sulphur etc. in the pollutant emission standard of vehicle exhaust and associated fuel product is substantially increased for this country
The content standard of thing.
It is an object of the present invention to provide the preparation of purifying agent for harmful gases and purification method and device in a kind of air-flow, for from
The nuisances such as sulfur dioxide, nitrogen oxides, carbon monoxide and VOCs (inclusion hydrocarbon) are removed in air-flow.
Content of the invention
Primary technical problem to be solved by this invention is to provide purifying agent for harmful gases in a kind of air-flow (hereinafter referred to as net
Agent) and preparation method thereof, for separately or concurrently removing nitrogen oxides, sulfur dioxide, carbon monoxide and VOCs from air-flow
Nuisances such as (hydrocarbon-containiproducts), active height, the high feature of removal efficiency.
Another technical problem to be solved by this invention is to provide purification method and the device of described cleanser, has behaviour
Make the feature that simple, treatment effeciency is high and operating cost is low.
The present invention solves the technical scheme that adopted of above-mentioned technical problem:A kind of gas purifying agent is it is characterised in that institute
The main component of the cleanser stated is (not comprise hydroxyl by iron (containing II), chlorine, calcium (II) (or magnesium II), hydroxyl (or water) and/or oxygen
Oxygen in base) mixing cpd that forms or complex compound, the mass percent of wherein each component is iron (containing II) 5-96%, chlorine 1-
80%, calcium (or magnesium) 1-80%, hydroxyl (or water) 0.5-40%, oxygen (not comprising the oxygen in hydroxyl) 0-40%.
A kind of preparation method of described cleanser, is characterized in that frerrous chloride and calcium oxide (or magnesia or hydrogen-oxygen
Change calcium or magnesium hydroxide) material adds mixed reaction vessel by a certain percentage, and (described chlorine is ferrous to be band to add suitable quantity of water
During crystallization water solid, such as four water frerrous chlorides, can not add water), it is sufficiently stirred for, so that material is mixed, this process protochloride
There is chemical reaction with calcium oxide (or magnesia or calcium hydroxide or magnesium hydroxide) in iron, obtain slimy solid product.
Above-mentioned hybrid reaction process releases heat, makes material have certain intensification.After question response finishes, then material thermal dehydration.Plus
Generally 50 DEG C -350 DEG C under hot temperature normal pressure, preferably 95 DEG C -300 DEG C, under negative pressure, heating-up temperature can be lower, makes in material
Excessive moisture volatilization is removed, and heating-up temperature is high, and dewatering time is just short, heats, during heating under negative pressure or vacuumized conditions
Between can be shorter, dehydration finish after the solid, powdery product that obtains, as a kind of cleanser of the present invention.Heating can be using electricity
The multiple means such as stove heat, heat-conducting medium heating, Electromagnetic Heating and heating using microwave, effect is suitable.Thermal dehydration process can be in nitrogen
Carry out in the inert gas shielding atmosphere such as gas, effect more preferably, to reduce ferrous oxidation.Heating-up temperature is low,
Not the content of oxygen (not comprising the oxygen in hydroxyl) relatively low (or not oxygen-containing) in described cleanser.
In the preparation method of cleanser of the present invention, wherein adopted using the oxide of calcium or the effect ratio of hydroxide
Better with the oxide of magnesium or the effect of hydroxide.Otheralkali metal or alkaline earth oxide or hydroxide may also be employed
Thing as the sub of calcium oxide, such as barium monoxide and barium hydroxide etc., other techniques ibid, the performance effect of obtained cleanser
Fruit is more weaker than the effect of above-mentioned employing calcium and the compound of magnesium.
Described calcium oxide (or magnesia or calcium hydroxide or magnesium hydroxide) or otheralkali metal or alkaline-earth metal oxygen
Compound or hydroxide dosage are generally 1 with the mol ratio of frerrous chloride material: 0.1-1: 10, preferably 1: 0.3-1: 5, described
When metal oxide or hydroxide are excessive, little to the performance impact of described cleanser.Concrete dosage also depends on air-flow
The concentration of middle nuisance, in air-flow, sulfur dioxide concentration is high, the ratio of calcium or magnesium just more greatly, nitrous oxides concentration height, iron dense
Degree is just high.
In the preparation method of cleanser of the present invention, also chlorine can be such as polymerized by other protochloride molysite derivative compounds
Changing ferrous iron etc. replaces chlorine ferrous, prepares as stated above, the effect of products therefrom is with above-mentioned preparation method.
A kind of preparation method of described cleanser is it is also possible to by ferrous hydroxide, calcium chloride (or magnesium chloride) and suitable quantity of water
Mixed preparing obtains, and wherein calcium chloride (or magnesium chloride) and ferrous hydroxide mol ratio are generally more than 0.5: 1, preferably 1.2: 1
~2: 1, the substantially same aforementioned process of other preparation technologies, but the performance of gained cleanser more above-mentioned with frerrous chloride and calcium oxide or
Calcium hydroxide for raw material prepare less better.
In the preparation process of cleanser of the present invention, the addition Main Function of described suitable quantity of water enables material wet
Profit, is sufficiently mixed between material and reacts, 1 to 10 times (mol ratios) of addition generally frerrous chloride, preferably 2-5 times.
In the preparation process of cleanser of the present invention, also can add a certain amount of before described material thermal dehydration technique
Acetone, butanone, ethanol or propyl alcohol equal solvent (as 5~50% volume ratios), and material stirring mixing, described solvent after heating
Volatilization, can increase the specific surface area of described cleanser, improve the utilization ratio of cleanser.
It is also possible to add the metal on a small quantity with catalytic action in material in the preparation process of cleanser of the present invention
Oxide, such as titanium dioxide, manganese dioxide, tungstic acid, vanadic anhydride, aluminum oxide or other transition elements oxide of mutuallies etc. are made
For auxiliary agent, addition no particular/special requirement, run-of-the-mill ratio for less than 20%, to promote the absorption of the nuisance in air-flow and to turn
Change, the effect of these metal oxides is about the same.
It is also possible to cleanser is supported on alumina particle, honeycomb pottery in the preparation process of cleanser of the present invention
On the carrier of the General Catalyst such as porcelain, effect quite, the preparation of preparation technology also similar associated catalysts, can be referring to related chemical industry
Handbook.
It is also possible to add a certain amount of adhesion-molded dose in the preparation process of cleanser of the present invention, such as calcium sulfate,
Calcium carbonate, silica and related salts and clay etc., quite, the addition of described forming agent is generally 1-50% (matter to effect
Amount ratio), pre-formed for described cleanser, such as the shapes such as ball, plate or ceramic honey comb can be made, its preparation technology similar to
The preparation of SCR denitration, specifically can be referring to related chemical industry handbook, and the thermal dehydration temperature of the cleanser after shaping is with aforementioned
Temperature range.Iron powder can also be added as compounding ingredient in material, but iron powder does not participate in reaction in cleanser preparation process.
The purification method of cleanser of the present invention is that the cleanser that above-mentioned preparation method is obtained imports gas-solid reaction
Cylinder, in gas-solid reaction cylinder, nitrogen oxides in air-flow, sulfur dioxide, carbon monoxide and VOCs (hydrocarbon-containiproducts) etc. have
Evil thing and described cleanser occur chemical reaction to be removed, thus reaching gas purification purpose.Wherein nitrogen oxides is by institute
The cleanser stated is reduced to nitrogen and is purified, and sulfur dioxide is cleaned agent chemisorbed and absorption is purified, carbon monoxide,
Hydrocarbon and VOCs etc. are purified by catalysis oxidation.
Gas-solid reaction cylinder of the present invention can using chemical engineering unit operation commonly use fixed bed, moving bed, ebullated bed,
The gas-solid contact reactor such as fluid bed and recirculating fluidized bed, can be using various ways such as following current, adverse current and cross-flows, and effect is substantially
Quite, specifically can be referring to related chemical industry equipment handbook.Taking recirculating fluidized bed reaction cartridge system as a example, described gas-solid reaction cylinder
Side lower part be provided with the gas feed connecting described air-flow, middle part be provided with cleanser particle add mouth, described cleanser
Grain feed postition quite, can be set using the mode such as power feed or strength charging, effect above the lower gas import of cylinder
It is equipped with air distributor, make gas-solid in cylinder be sufficiently mixed contact, the top of cylinder is provided with connecting tube, and described air-flow passes through even
Adapter is connected with gas-solid separator, and after gas-solid separator gas solid separation, air-flow is discharged from the top of gas-solid separator, cleanser
Particle is discharged from gas-solid separator bottom, and wherein Partial cleansing dose can return to participate in reaction (also can not return) in cylinder, specifically may be used
Described material is adjusted according to the extent of reaction and returns the ratio (scope can be 0-100%) participating in reaction in cylinder.
Generally 25 DEG C -350 DEG C of the purification temperature scope of the cleanser in gas-solid reaction cylinder of the present invention, preferably
Temperature range is 100 DEG C -300 DEG C.Gas flow temperature as entered gas-solid reaction cylinder is less than 50 DEG C, needs in advance described purification
Agent preheating temperature to more than 100 DEG C, preferably 150 DEG C -250 DEG C of heated perimeter, make cleanser add after being activated gas-solid anti-
Answer cylinder.The gas-solid contact time of described nuisance course of reaction in described reaction tube is generally more than 0.2s, time of contact
Long, clearance is high, preferably 0.5s-30s.Cleanser (being calculated with ferrous iron, similarly hereinafter) and the reaction mole about 1 of nitrogen oxides:
1, the reaction mole about 1: 1 of cleanser (being calculated with calcium or magnesium, similarly hereinafter) and sulfur dioxide, actual mechanical process, the throwing of cleanser
Dosage the operation such as can require according to the specific surface area of cleanser, concentration of harmful substance, gas flow temperature, gas-solid contact time and clearance
Parameter and determine.For recirculating fluidized bed gas-solid reaction cylinder, the mol ratio of cleanser dosage and nitrogen oxides and sulfur dioxide
Typically it is more than 1, the removal effect of the bigger nuisance of mol ratio is better, but energy consumption increases, and is preferentially taken as 5-100, for solid
The reactors such as fixed bed, moving bed and ebullated bed, no particular requirement, optionally add.The particle diameter of described cleanser and structure can roots
Select according to different reactor, no particular/special requirement, fluid bed, moving bed and ebullated bed can adopt particulate burning purifying agent, average grain diameter one
As be 0.01mm-5mm.Fixed bed can be molded cleanser using spherical, flat board or ceramic honey comb shape etc..Oxygen in air-flow and moisture
Deng other contents, the removal of nuisance is affected less.
Reacted solid product process further after recoverable, reacted solid product can be dissolved in clear water
The byproducts such as iron chloride are reclaimed it is also possible to the byproducts such as iron oxide are obtained by heating further after equal solvent.
Air-flow of the present invention is mainly the flue gas that fuel combustion process produces, and including all kinds of vehicle exhausts, may also be
The relevant gas flow that other industrial process produce.
Compared with prior art, it is an advantage of the current invention that:Using described cleanser at a certain temperature can simultaneously with
The nuisances such as the nitrogen oxides in air-flow, sulfur dioxide, carbon monoxide and VOCs react and are removed, wherein nitrogen oxides
It is reduced to nitrogen by described cleanser to be purified, sulfur dioxide is cleaned agent chemisorbed and absorption is purified, hydrocarbon
Compound and VOCs etc. are purified by catalysis oxidation, have cost of investment and operating cost is low, simple to operate, treatment effeciency
Height, is suitable for promoting the use of.
Brief description
Fig. 1 is the device knot of the purification method of purifying agent for harmful gases in a kind of air-flow in embodiment 10-13 in the present invention
Structure schematic diagram.
Fig. 2 is that the apparatus structure of the purification method of purifying agent for harmful gases in a kind of air-flow in embodiment 14 in the present invention shows
It is intended to.
Fig. 3 is that the apparatus structure of the purification method of purifying agent for harmful gases in a kind of air-flow in embodiment 15 in the present invention shows
It is intended to.
In figure:1 gas feed;2 gas distributors;3 cleansers add mouth;4 cylinders;5 connecting tubes;6 gas vents;7 gas
Solid separator;8 cleanser return ports;9 cleanser outlets;10 access holes;11 bottom cleanser outlets;12 gas-solid reactions
Area;13 cleanser recovery areas;14 cleanser filling beds.
Specific embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
In a kind of air-flow, the recirculating fluidized bed gas-solid reaction wound packages of the purification method of purifying agent for harmful gases is put as Fig. 1 institute
Show.This device includes cylinder (4), and the side lower part of cylinder (4) is provided with the gas feed (1) connecting air-flow, under cylinder (4)
Being provided with air distributor (2) above portion's air flow inlet makes gas-solid in cylinder be sufficiently mixed, and middle part is provided with solid purificant and adds
Mouth (3), the connecting tube (5) that the top of cylinder (4) is passed through to arrange is connected with gas-solid separator (7), and the top of gas-solid separator 7 sets
It is equipped with gas vent (6), the bottom of gas-solid separator (7) is provided with solid purificant outlet (9), and cleanser return port
(8) connect with cylinder (4), cylinder (4) middle and lower part and bottom are also respectively provided with access hole (10) and ttom of pipe cleanser outlet
(11).
The recirculating fluidized bed gas-solid reaction of the purification method of purifying agent for harmful gases in a kind of air-flow according to Fig. 1
Wound packages is put, and its processing technological flow is pending air-flow to be imported cylinder (4) by gas feed (1), through gas distributor (2)
After adding the cleanser that mouth (3) adds to mix by cleanser, occur gas-solid adsorption redox reaction, the air-flow after purification from
The connecting tube (5) on cylinder top enters gas-solid separator (7) and carries out gas solid separation, and air-flow is discharged from gas vent (6), and part is not anti-
The cleanser answered can be returned by cleanser return port (8) and continue in cylinder (4) to participate in reaction, and remainder is arranged by cleanser
Outlet (9) is discharged, and cylinder bottom is also equipped with bottom cleanser outlet (11) and discharges unnecessary cleanser simultaneously.
Embodiment 1:A kind of preparation method of described cleanser is as follows:Frerrous chloride, calcium hydroxide and water are pressed about 1.3: 1
: 3 (mol ratio, similarly hereinafter) ratio adds mixed reaction vessel, and is sufficiently stirred for, and so that material is mixed, and question response finishes afterwards (about
Need more than 30 minutes), then heated material after being filled with nitrogen into described mixing reactor, and stir, heating-up temperature is about
50-60 DEG C, about 4 hours time, so that the excessive moisture in material is volatilized and remove, the powdery solid product obtaining is one kind originally
The described cleanser of invention, the screened solid purificant particle obtaining required particle diameter is standby.
Embodiment 2:A kind of preparation method of described cleanser is as follows:Four water frerrous chlorides and lime powder are pressed about 1:
1.5 ratios add mixing reactor, and are sufficiently stirred for, and so that material is mixed, and question response finishes rear (about needing more than 30 minutes),
Then heated material after being filled with nitrogen into described mixing reactor, and stir, heating-up temperature is about 150 DEG C, and the time is about 2
Hour, so that the excessive moisture in material is volatilized and remove, the powdery solid product obtaining is one kind is cleanser of the present invention,
The screened solid purificant particle obtaining required particle diameter is standby.
Embodiment 3:A kind of preparation method of described cleanser is as follows:Four water frerrous chlorides and magnesium oxide powder are pressed about 1:
1.3 ratios add mixing reactor, and are sufficiently stirred for, and so that material is mixed, and question response finishes rear (about needing more than 30 minutes),
Then heated material after being filled with nitrogen into described mixing reactor, and stir, heating-up temperature is about 200 DEG C, and the time is about 1
Hour, so that the excessive moisture in material is volatilized and remove, the powdery solid product obtaining is one kind is cleanser of the present invention,
The screened solid purificant particle obtaining required particle diameter is standby.
Embodiment 4:A kind of preparation method of described cleanser is as follows:Frerrous chloride, magnesium hydroxide and water are pressed about 1.3: 1
: 3 (mol ratio, similarly hereinafter) ratio adds mixed reaction vessel, and is sufficiently stirred for, and so that material is mixed, and question response finishes afterwards (about
Need more than 30 minutes), then heated material after being filled with nitrogen into described mixing reactor, and stir, heating-up temperature is about
95 DEG C, the time is about 4 hours, so that excessive moisture in material is volatilized and removes, the powdery solid product obtaining be a kind of this
Bright described cleanser, the screened solid purificant particle obtaining required particle diameter is standby.
Embodiment 5:A kind of preparation method of described cleanser is as follows:Ferrous hydroxide, calcium chloride and water are pressed about 1: 2: 3
Ratio adds mixing reactor, and is sufficiently stirred for, and so that material is mixed, and question response finishes rear (about needing more than 30 minutes), so
Heated material after being filled with nitrogen into described mixing reactor afterwards, and stir, heating-up temperature is about 300 DEG C, and it is little that the time is about 1
When, so that the excessive moisture in material is volatilized and remove, the powdery solid product obtaining is a kind of for cleanser of the present invention, warp
The solid purificant particle that screening obtains required particle diameter is standby.
Embodiment 6:A kind of preparation method of described cleanser is as follows:Seven or four water frerrous chloride in above-described embodiment 2
After terminating with calcium oxide reaction, add the acetone of volume of material about described in 20%, stir, then to described mixing reactor
Inside it is filled with heated material after nitrogen, heating-up temperature is about 95 DEG C, the time is about 3 hours, makes the excessive moisture in material and acetone
Volatilization removes, the product of the powdery solid obtaining is a kind of cleanser of the present invention, the screened required particle diameter that obtains
Solid purificant particle is standby.
Embodiment 7:A kind of preparation method of described cleanser is as follows:Adding four water frerrous chlorides in above-described embodiment 2
While with calcium oxide material, add the titanium dioxide solids powder (anatase titanium dioxide) accounting for total material 5% (mass ratio) together, fill
Divide stirring, so that material is mixed, question response finishes rear (about needing more than 30 minutes), is then filled with into described mixing reactor
Heated material after nitrogen, heating-up temperature is about 300 DEG C, and the time is about 1 hour, so that the excessive moisture in material is volatilized and removes, obtains
The powdery solid product arriving is cleanser of the present invention, and the screened solid purificant particle obtaining required particle diameter is standby
With.
Embodiment 8:A kind of preparation method of described cleanser is as follows:Four water frerrous chlorides in above-described embodiment 2 and
In the material obtaining after calcium oxide reaction, add the Woelm Alumina particulate vector that isopyknic diameter is about 3mm, stirring is mixed
Close, make described material be supported on described carrier surface, be then filled with after nitrogen into described mixing reactor, evacuate heating under reduced pressure
Material, heating-up temperature is about 200 DEG C, and the time is about 1 hour, so that the excessive moisture in material is volatilized and removes, the solid obtaining
Grain product is a kind of cleanser of the present invention.
Embodiment 9:A kind of preparation method of described cleanser is as follows:Four water frerrous chlorides in above-described embodiment 2 and
In the material that obtains after calcium oxide reaction, add the calcium sulphate dihydrate as forming agent, the dosage of described calcium sulphate dihydrate with
The mol ratio of frerrous chloride material is about 1: 1, and after stirring, and (aperture is about Ф to make the honeycomb of Ф 50mm × 50mm
3mm) cylinder, then heated dehydration under nitrogen protection, heating-up temperature is about 150 DEG C, and the time is about 2 hours, makes in material
Excessive moisture volatilization remove, the ceramic honey comb shape cleanser product obtaining, that is, a kind of is cleanser of the present invention.
Embodiment 10:The recirculating fluidized bed gas-solid reaction wound packages of the purification method of purifying agent for harmful gases in a kind of air-flow
Put as shown in Figure 1.The a diameter of Ф 60mm of described recirculating fluidized bed gas-solid reaction cylinder, a height of 2500mm, cylinder material be 316L not
Rust steel.In air-flow, the concentration of nitrogen oxides (nitric oxide is about 95%) is 500ppm, and oxygen content is about 8% (volume), water
Content is divided to be about 10% (volume), remaining is nitrogen, gas flow is about 5m3(in reaction tube, gas-solid contact time is about 1- to/h
3s).Using the cleanser obtained by embodiment 1, cleanser average grain diameter is about 0.5mm, and addition is about 2kg/h.Cleanser
Feed as mechanical metering feeding.Separate solid particle after being reacted through gas-solid separator (adopting cyclone separator) and do not return cylinder
Interior.When inlet air flow temperature is respectively 25 DEG C, (now, cleanser is preheating to 150 before adding gas-solid reaction cylinder in feed bin
DEG C), 100 DEG C, 200 DEG C, 250 DEG C and when 300 DEG C, experimental result obtains gas vent NOxConcentration respectively 451ppm,
298ppm, 174ppm, 185ppm and 279ppm.
Embodiment 11:The recirculating fluidized bed gas-solid reaction wound packages of the purification method of purifying agent for harmful gases in a kind of air-flow
Put as shown in Figure 1.The a diameter of Ф 60mm of described recirculating fluidized bed gas-solid reaction cylinder, a height of 2500mm, cylinder material be 316L not
Rust steel.In air-flow, the concentration of sulfur dioxide is 550ppm, and oxygen content is about 8% (volume), and moisture is about 10% (body
Long-pending), remaining is nitrogen, and gas flow is about 5m3/ h (in reaction tube, gas-solid contact time is about 1-3s).Using embodiment 2 institute
Prepared cleanser, cleanser average grain diameter is about 0.5mm, and addition is about 1kg/h.Cleanser feed for machinery measure into
Material.Separate solid particle after being reacted not returning in cylinder through gas-solid separator (adopting cyclone separator).When inlet air flow temperature
When degree is respectively 50 DEG C, 100 DEG C, 200 DEG C, 250 DEG C and 300 DEG C, experimental result obtains gas vent SO2Concentration is respectively
241ppm, 135ppm, 168ppm, 295ppm and 375ppm.
Embodiment 12:The recirculating fluidized bed gas-solid reaction wound packages of the purification method of purifying agent for harmful gases in a kind of air-flow
Put as shown in Figure 1.The a diameter of Ф 60mm of described recirculating fluidized bed gas-solid reaction cylinder, a height of 2500mm, cylinder material be 316L not
Rust steel.In air-flow, the concentration of nitrogen oxides (nitric oxide is about 95%) is 500ppm, and the concentration of sulfur dioxide is 550ppm,
VOCs (comprising hydrocarbon, alcohol and ketone and ester etc., predominantly hydrocarbon) concentration is about 150mg/m3, oxygen content about 6% (body
Long-pending), moisture is about 8% (volume), and remaining is nitrogen, and gas flow is about 5m3(in reaction tube, gas-solid contact time is about for/h
For 1-3s).Using the cleanser obtained by embodiment 2, cleanser average grain diameter is about 0.5mm, and addition is about 2-3kg/h.
Cleanser feeds as mechanical metering feeding.Through gas-solid separator (adopting cyclone separator) separate reacted after solid particle not
Return in cylinder.When inlet air flow temperature is 160 DEG C -180 DEG C, experimental result obtains gas vent NOxConcentration is 159ppm, SO2
Concentration is 157ppm, and VOCs concentration is 65mg/m3.
Embodiment 13:It is respectively adopted the cleanser obtained by embodiment 3,4,5,6 and 7, other conditions are with embodiment 12.Real
Test result as follows:
During using cleanser obtained by embodiment 3, the gas vent NO recordingxConcentration is 159ppm, SO2Concentration is
179ppm, VOCs concentration is 73mg/m3;During using cleanser obtained by embodiment 4, the gas vent NO recordingxConcentration is
168ppm, SO2Concentration is 190ppm, and VOCs (comprising hydrocarbon, alcohol and ketone and ester etc., predominantly hydrocarbon) concentration is 85mg/
m3;During using cleanser obtained by embodiment 5, the gas vent NO recordingxConcentration is 271ppm, SO2Concentration is 293ppm,
VOCs concentration is 99mg/m3;During using cleanser obtained by embodiment 6, the gas vent NO recordingxConcentration is 145ppm,
SO2Concentration is 166ppm, and VOCs concentration is 58mg/m3;During using cleanser obtained by embodiment 7, the gas vent recording
NOxConcentration is 131ppm, SO2Concentration is 139ppm, and VOCs concentration is 42mg/m3.
Embodiment 14:The gas-solid counter-flow moving bed reaction wound packages of the purification method of purifying agent for harmful gases in a kind of air-flow
Put as shown in Figure 2.This device includes cylinder (4), and cylinder (4) bottom is provided with gas feed (1), and top is provided with cleanser and adds
Entrance (3) and gas vent (6), bottom is provided with cleanser outlet (9), and gas feed (1) is anti-through the gas-solid in cylinder (4)
Answer area (12) to connect with gas vent (6), described cleanser add mouth (3) through the gas-solid reaction area (12) in cylinder (4) and
Cleanser recovery area (13) is connected with cleanser particle discharge ports (9).Described cylinder (4) caliber is Ф 60mm, a height of
1500mm, cylinder material is 316L stainless steel, and the effective depth of gas-solid reaction area (12) is about 1000mm.
Its processing technological flow is pending air-flow to be entered cylinder (4) by gas feed (1) add with by cleanser
There is the reaction of gas-solid redox chemistry in gas-solid reaction area (12) in the cleanser that mouth (3) adds, the air-flow after purification is from gas
Outlet (6) is discharged, and after reaction, solid particle passes through cleanser outlet (9) discharge after solid purificant recovery area (13).
Air-flow is air, and relative humidity is about 70%, and in air-flow, nitric oxide concentration is 300ppm, the concentration of sulfur dioxide
For 550ppm, VOCs concentration is about 200mg/m3(comprising hydrocarbon, alcohol and ketone and ester etc., predominantly hydrocarbon).Using enforcement
The cleanser that example 7 is obtained, average grain diameter is about 0.5mm, and cleanser addition is about 2kg/h.Reaction tube airflow inlet gas temperature
Degree respectively may be about 150 DEG C, 250 DEG C and 300 DEG C, gas flow about 1m3/ h, in reaction tube, gas-solid contact time is about 10-15s.
Experimental result is as follows:When gas inlet temperature is 150 DEG C, the gas vent NO concentration recording is 80ppm, SO2Concentration is
140ppm, VOCs concentration is 95mg/m3;When gas inlet temperature is 250 DEG C, the gas vent NO concentration recording is 78ppm, SO2
Concentration is 183ppm, and VOCs concentration is 75mg/m3;When gas inlet temperature is 300 DEG C, the gas vent NO concentration recording is
81ppm, SO2Concentration is 329ppm, and VOCs concentration is 35mg/m3.
Embodiment 15:In a kind of air-flow the fixed bed gas-solid reaction wound packages of the purification method of purifying agent for harmful gases put as
Shown in Fig. 3.This device includes cylinder (4), and cylinder (4) bottom is provided with gas feed (1), and gas feed is provided with above (1)
Air distributor (2), is cleanser filling bed (14) above air distributor (2), the top setting of cleanser filling bed (14)
Cleanser is had to add mouth (3), bottom to be provided with cleanser outlet (9), the top of cylinder (4) also sets up gas vent (6), gas
Body import (1) is connected with gas vent (6) with the void gas passage of cleanser filling bed (14) through air distributor (2), institute
The cleanser stated adds mouth (3) to connect with cleanser filling bed (14) respectively with cleanser outlet (9).
Its processing technological flow is through air distributor the pending air-flow containing nuisance by gas feed (1)
(2) import cleanser filling bed (14), in described cleanser filling bed (14), nuisance and cleanser occur gas-solid chemistry
Reaction and be removed, the gas vent (6) from reaction tube top for the air-flow after purification is discharged, and after reaction, the cleanser of actual effect can be by
Cleanser outlet (9) is periodically discharged and is changed.
The described a diameter of Ф 60mm of cylinder (4), a height of 1500mm, material is 316L stainless steel.It is respectively adopted embodiment 8
The alumina support cleanser prepared with 9 and honeycomb moulding cleanser, the bulk density of alumina support cleanser is about
1500kg/m3, in two kinds of situation reaction tubes, the packed height of cleanser is each about 500mm, reaction drum outer wall insulation.
Test air-flow is the air-flow of simulated automotive tail gas, and the wherein inlet concentration of pollutant is respectively nitrogen oxides about
200ppm, sulfur dioxide about 50ppm, carbon monoxide are about 50mg/m3It is about 150mg/m with hydrocarbon3, gas flow is about
1m3/ h, gas time of staying in reaction tube is about 5s-15s, and reaction tube air-flow gas inlet temperature is about 200-220 DEG C.Survey
Employing alumina support cleanser when, after purification the exit concentration of pollutant be respectively nitrogen oxides about 15ppm, sulfur dioxide
About 21ppm, carbon monoxide are about 5mg/m3It is about 17mg/m with hydrocarbon3;During using honeycomb moulding cleanser, after purification
The exit concentration of pollutant respectively nitrogen oxides about 4ppm, sulfur dioxide about 12ppm, carbon monoxide are about 2mg/m3With hydrocarbon
Compound is about 4mg/m3.Amount due to the cleanser of fixed bed reaction cylinder addition is fixing, nuisance therefore in air-flow
Clearance is varied from the reaction consumption of cleanser in cylinder, when the gas vent pollutant levels recording are maximum material removal rate
Concentration.
It should be noted that above example is merely to illustrate technical scheme, protection scope of the present invention is not
It is limited to this.For a person skilled in the art, all within the spirit and principles in the present invention, to described in each embodiment
Technical scheme is modified, or carries out any equivalent, modification, changes and improvements etc. to some technical characteristics therein,
Should be included within the scope of the present invention.
Claims (10)
1. in a kind of air-flow purifying agent for harmful gases it is characterised in that the main component of described cleanser be by iron (containing II),
Mixing cpd or complexing that chlorine, calcium (1I) (or magnesium II), hydroxyl (or water) and/or oxygen (not comprising the oxygen in hydroxyl) form
Thing, the mass percent of wherein each component is iron (containing II) 5-96%, chlorine 1-80%, calcium (or magnesium) 1-80%, hydroxyl (or water)
0.5-40%, oxygen (not comprising the oxygen in hydroxyl) 0-40%.
2. a kind of cleanser according to claim 1 is it is characterised in that the preparation method of described cleanser is chlorination
(described frerrous chloride is the band crystallization water for ferrous iron, calcium oxide (or magnesia or calcium hydroxide or magnesium hydroxide) and suitable quantity of water
During solid, can not add water) there is the solid product that obtains after chemical reaction, the product obtaining after heated dehydration after mixing.
3. a kind of cleanser according to claim 1 is it is characterised in that the preparation method of described cleanser is hydrogen-oxygen
Change ferrous, calcium chloride (or magnesium chloride) and suitable quantity of water mixed preparing obtains solid product, the product obtaining after heated dehydration, its
Middle calcium chloride (or magnesium chloride) and ferrous hydroxide mol ratio are generally more than 0.5: 1.
4. the preparation method of the cleanser according to Claims 2 or 3 is it is characterised in that described cleanser preparation process
In, add acetone, butanone, ethanol or the propanol solvent of 5~50% (volume ratios) before described solid product thermal dehydration;?
Metal oxide oxidation catalyst auxiliary agent can be added in described solid product, including titanium dioxide, manganese dioxide, tungstic acid,
Vanadic anhydride or aluminum oxide, content is less than 20% (mass ratio);The addition of described suitable quantity of water is described protochloride iron
1 to 10 times (mol ratios).
5. the preparation method of cleanser according to claim 2 it is characterised in that described calcium oxide (or magnesia or
Calcium hydroxide or magnesium hydroxide) the mol ratio of dosage and frerrous chloride material be 1: 0.1-1: 10.
6. according to claim 1 or cleanser described in 2 or 3 it is characterised in that cleanser is supported on the carrier of General Catalyst
On, including alumina particle and ceramic honey comb;Can also described cleanser is pre-formed, including ball-type, board-like or honeycomb
Ceramic-like structure.
7. a kind of cleanser according to claim 1 or 2 or 3 is it is characterised in that in the main component of described cleanser
Calcium (II) (or magnesium II) adopts otheralkali metal or alkaline earth oxide or hydroxide, including barium monoxide and barium hydroxide,
Other components and content are constant.
8. the cleanser according to Claims 2 or 3 or 4 preparation method it is characterised in that described solid product plus
Heat dehydration, heating-up temperature is 50 DEG C -350 DEG C, and heating is using heating by electric cooker, heat-conducting medium heating, Electromagnetic Heating or heating using microwave.
9. a kind of purification method having purifying agent for harmful gases in air-flow is it is characterised in that import described cleanser gas-solid anti-
Answer cylinder, in gas-solid reaction cylinder, nitrogen oxides in air-flow, sulfur dioxide, carbon monoxide and VOCs (hydrocarbon-containiproducts) with
Described cleanser occurs gas-solid reaction to be removed, and purification temperature scope in gas-solid reaction tower for the described air-flow is 25 DEG C-
350℃.
10. the device of purification method according to claim 9 is it is characterised in that described gas-solid reaction cylinder adopts chemical industry
The unit general gas-solid contact reactor of operation, including fixed bed, moving bed, ebullated bed, fluid bed or recirculating fluidized bed gas-
Gu contact reactor.
Priority Applications (8)
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CN201610906058.1A CN106377997A (en) | 2016-10-17 | 2016-10-17 | Preparation of harmful gas purifying agent in air flow, and purification method and device by using purifying agent |
US16/336,099 US11911740B2 (en) | 2016-10-14 | 2017-10-13 | Noxious gas purificant and its preparation and purification method thereof |
AU2017344205A AU2017344205B2 (en) | 2016-10-14 | 2017-10-13 | Gas detoxification agent, and preparing and detoxification methods thereof |
CN201780010197.9A CN109715269B (en) | 2016-10-14 | 2017-10-13 | Harmful gas purifying agent for adsorbing and removing nitrogen oxides in gas flow within temperature range of 60-500 DEG C |
JP2019519365A JP7120650B2 (en) | 2016-10-14 | 2017-10-13 | Purification agent manufacturing method, purification method using purification agent, and purification agent regeneration method |
CA3038760A CA3038760C (en) | 2016-10-14 | 2017-10-13 | A noxious gas purificant and its preparation and purification method thereof |
PCT/CN2017/106121 WO2018068765A1 (en) | 2016-10-14 | 2017-10-13 | Gas detoxification agent, and preparing and detoxification methods thereof |
US18/332,712 US20240001332A1 (en) | 2016-10-14 | 2023-06-10 | Noxious gas purificant and its preparation and purification method thereof |
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WO2018068765A1 (en) * | 2016-10-14 | 2018-04-19 | 黄华丽 | Gas detoxification agent, and preparing and detoxification methods thereof |
AU2017344205B2 (en) * | 2016-10-14 | 2020-11-12 | Liwei Huang | Gas detoxification agent, and preparing and detoxification methods thereof |
US11911740B2 (en) | 2016-10-14 | 2024-02-27 | Liwei Huang | Noxious gas purificant and its preparation and purification method thereof |
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