CN110479303A - A kind of dry method solid desulphurization denitration catalyst and its desulfurization denitrification agent - Google Patents
A kind of dry method solid desulphurization denitration catalyst and its desulfurization denitrification agent Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
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Abstract
A kind of dry method solid desulphurization denitration catalyst and its desulfurization denitrification agent, the present invention relates to field of gas treatment.For the performance for improving desulphurization denitration, a kind of catalyst provided by the invention, preparation method are as follows: more than one mass ratio being accounted for 15.0-396.0 parts of mantoquita and/or more than one mass ratio accounts for 32.0-48.0 parts of manganese salt, mass ratio accounts for 10.0-30 parts of KMnO4And mass ratio accounts for 100.0-900.0 parts of sodium carbonate liquor and is distributed in solvent and forms slurry, stirs, after product is filtered, washed, is dried, ground, in air atmosphere, calcination is formed under the conditions of 300 DEG C -350 DEG C.The beneficial effects of the present invention are: 1, desulphurization denitration purpose realization complicated flue gas condition under avoids relying on equipment and operating condition complexity caused by accurate adjusting nitrogenous reducing agent；2, desulfurization denitrification agent transport provided by the invention, storage, replacement are convenient；3, catalyst is properly added in alkaline base-material, can play desulfurization and denitration.
Description
Technical field
The present invention relates to field of gas treatment, specifically a kind of for purifying the dry desulfurization denitration of low-temperature zone flue gas
Agent.
Background technique
It reduces sulfureous in flue gas oxide and nitrogen oxides is the important channel for reducing atmosphere pollution, document report and industrial institute
There are a variety of choosings then schemes for the denitration temperature range taken and the denitration mode taken, such as: non-selective reductant denitration
It (SNCR) in temperature is about usually that 800 DEG C~950 DEG C ranges carry out.It is applicable according to selective catalytic reduction (SCR) catalyst
Flue-gas temperature range is different, SCR catalyst can be divided into high temperature (450 DEG C -600 DEG C or more), medium temperature (320 DEG C -450 DEG C) and
Low temperature (120 DEG C -300 DEG C).In addition, there is also the research and probes of the SCR denitration of lower temperature.Currently, steel-making, glass
The flue gas that production plant discharges 100 DEG C or so contains the SO that concentration is higher than minimum discharge limit value2And NO, development effectiveness is significant, has
There is the desulfurization denitrification agent of longer life to be of great significance.
Currently, the typical tool low temperature catalyst of one kind of report is manganese systems SCR catalyst.According to there is non-loaded feelings
Condition, this catalyst are divided into two kinds again: support type and non-loading type.Unsupported manganese systems SCR catalyst activity is improved, is usually to mix
Miscellaneous other metallic elements, such as Kang M et al. (Cu-Mn mixed oxides or low temperature NO
reduction with NH3[J] Catalysis Today, 2006,111 (3-4): 236-241) with nitric hydrate copper and hydration
Manganese nitrate is prepared for the complex copper Mn catalyst with high reaction activity as raw material, using co-precipitation and calcination method, uses
NO(500ppm)、NH3(500ppm)、O2(5Vol.%) and nitrogen carrier gas are 3000h in air speed as simulated flue gas-1, temperature
Realize the high conversion rate of NO in 90% under the conditions of being 50 DEG C -250 DEG C.For another example Long RQ et al. (Low temperature
selective catalytic reduction(SCR)of NO with NH3over Fe–Mn based catalysts[J]
Chemical Communications, 2002:452-453) with nitric hydrate iron, it is hydrated manganese acetate, is hydrated copper acetate, nitric acid
Oxygen zirconium, ammonium carbonate are that equimolar ratio feeds intake according to iron-manganese-third element, are by coprecipitation as raw material
Ferrimanganic, ferrimanganic zirconium, the ferrimanganic titanium low temperature catalyst of column, with NO (1000ppm), NH3(1000ppm)、O2(2%), helium carrier gas is made
It is 1500h in air speed for simulated flue gas-1, temperature be 80 DEG C -180 DEG C under the conditions of reach: under the conditions of 80 DEG C, the conversion ratio of NO is
68-74%；Under the conditions of 120 DEG C, the conversion ratio of NO is close to 100%.However it is directed to " pure MnOx", in 80 DEG C of -180 DEG C of conditions
Under, the conversion ratio of NO is 72-93%, and generates the N of 8%-35%2O, when introducing H in above-mentioned simulated flue gas2O
(2.5Vol.%) has an adverse effect for the denitration efficiency of catalyst, but works as operating temperature under the conditions of 160 DEG C -180 DEG C,
The conversion ratio of NO is still close to 100%, and even if in H2O (2.5Vol.%) and SO2(37.5ppm or 1000ppm) is common
In the presence of in the case of, the conversion ratio of NO, which has no, to be significantly affected.Non-loading type SCR catalyst relatively above, support type manganese systems SCR are urged
The research of agent is related to Al2O3、TiO2, the carriers such as attapulgite.These carriers are capable of providing relatively high specific surface area, or
Sulfur resistance is provided.Such as Ettiredyy P R et al. (Surace characterization studies of
TiO2supported manganese oxide catalysts for low temperature SCR of NO with
NH3, Applied Catalysis B:Environmental, 2007, (26): 123-134) distinguished using manganese nitrate aqueous solution
With anatase TiO2(Hombikat), rutile TiO2(Kemira, 100% rutile), compound phase TiO2(Degussa P-25,
80% anatase；20% rutile) mixing, after evaporating moisture content, becomes low-temperature SCR catalyst by drying and calcination, will contain
O2(2.0Vol.%), NH3(400ppm), NO (400ppm), helium are carrier gas as simulated flue gas, are 50000h in air speed-1,
Under the conditions of temperature is 175 DEG C: for Mn/TiO2(Hombikat) content is the catalyst of 16.67wt.%, the conversion ratio of NO
Reach 94%；For Mn/TiO2(Kemira) catalyst, there is closely similar trend.However, in terms of catalytic activity,
Mn/TiO2(Degussa P-25) performance is poor compared with the above two.Simulate the H that 11Vol.% is introduced in gas2O, by for 24 hours
Burn-in test show the conversion ratio and N of NO2Selectivity do not change.
A kind of scheme of the desulphurization denitration of the flue gas of another kind of low-temperature zone reported in the literature is: using alkaline-earth metal oxide
Object, hydroxide or carbonate etc. are used as carrier, add oxidant to improve desulfurization effect.Such as: application No. is
The patent disclosure original text of CN201610964889.4 and CN201610966733.X and application No. is the special of CN201620222745.7
Benefit describe " using at least one of calcium hydroxide, calcium carbonate, magnesium hydroxide, magnesium carbonate, sodium carbonate or sour hydrogen sodium, or
Remixing the graininess denitrfying agent that a small amount of sodium hypochlorite or potassium permanganate are formed has good desulfurization and denitration effect.Again
Such as: application No. is the patent disclosure original texts of CN201610164989.9 to describe using calcium hydroxide, calcium carbonate, magnesium hydroxide, carbon
At least one of sour magnesium, sodium carbonate or sodium bicarbonate, and it is added binder 0.1wt.%~10wt.%, 5wt.%~
The diatomite or kaolin of 10wt.%, the ceria of 0.2wt.%~1wt.% and the sodium chlorate of 1wt.%~50wt.%
Or the desulfurization denitrification agent that potassium permanganate is prepared.The above patent, which describes the characteristics of these desulfurization denitrification agents, is: " ... efficiently
Desulphurization denitration material have good removal effect in extensive temperature range, even if at 0 degree of temperature, removal efficiency also exists
80% or more.With temperature rising, desulfuration efficiency has the tendency that rising.At each temperature desulfuration efficiency easily reach 90% and
90% or more ".
Total chemical action effect of above-mentioned first kind SCR reaction is: NH3As reducing agent, in O2Under the conditions of existing also
Former NO produces N2And H2O.From above-mentioned document can be seen that these SCR catalysts activity with element combinations and proportion, prepare item
The factors such as the structure of part, carrier are closely related.Also, about sulfur poisoning-resistant and research in terms of the service life not system.Cause this
The substance of a little catalyst failures includes: alkali metal ion, sulfate, vapor etc..Therefore, it is realized in engineer application higher de-
Nitre efficiency is necessarily required to the even concentration of reducing agent, and operating temperature can be intended to match proper in terms of anti-poisoning.It is this more
The complexity that kind factor restricts increases the risk of the escaping of ammonia generation, while the design for also having aggravated SCR catalyst system equipment is difficult
Degree and (Zhu Jianjun, SCR device structure, which designs and produces, to be controlled several of the escaping of ammonia rate in installation and arrange to the difficulty of process conditions control
Apply, under coal-burning power plant's minimum discharge situations in 2016 SCR denitration system operational management and the escaping of ammonia monitoring, air preheater blocking with it is low
Warm economizer improved technology exchanges conference Papers collection, 2016:143-149).
The advantage of above-mentioned second class desulfurization denitrification agent is not need NH3As reducing agent, this avoids vanadium titanium-based or manganese
Base catalyst due to being poisoned or fail caused by the escaping of ammonia problem.Meanwhile the alkaline matter containing alkaline earth or alkali metal element
As absorbent, then stronger neutralization, absorption may be played for oxysulfide and the nitrogen oxides.However, existing
Discovery doping NaClO, KMnO in reality4、CeO2Alkaline base-material to SO in flue gas2And/or the removing ability of NO is still not ideal enough.This
It is huge to will cause desulfurization denitrification agent consumption.
Summary of the invention
The present invention is directed to the desulphurization denitration of low-temperature flue gas, uses for reference the scheme of dry method or semi-dry desulphurization, with calcic and/or
Alkaline matter containing magnesium is added to the catalyst containing manganese and copper, it will be apparent that improve the efficiency of desulfurization denitrification agent as carrier.And
And these desulfurization denitrification agents can be used alone as desulfurization or denitration purpose.
The present invention by denitration temperature section be divided into high temperature (450 DEG C or more), medium temperature (320 DEG C -450 DEG C) and low temperature (300 DEG C with
Under), technical solution presented below is suitable for low temperature.
One of the objects of the present invention is to provide a kind of dry method solid desulphurization denitration catalyst, the catalyst be containing
It is formed after mantoquita and/or manganese salt, potassium permanganate and sodium carbonate mixing in calcination.
Specifically, catalyst is the mixture and/or compound of cupric, manganese and oxygen element, the preparation method is as follows: it is preferred that
Under room temperature and stirring, more than one mass ratio is accounted for the mantoquita and/or more than one quality of 15.0-396.0
Ratio accounts for 32.0-48.0 manganese salt, mass ratio accounts for the KMnO of (preferably 20.0) 10-304And mass ratio accounts for 100.0-900.0
Being distributed to solvent, (preferred mass ratio accounts for the sodium carbonate liquor (preferred sodium carbonate liquor mass percent concentration is 20.0%) of part
1000 water) in formed slurry, stir 5~24 hours, after product is filtered, washed, is dried, being ground, in air atmosphere, in
Calcination (preferred calcination time is 5~8 hours) forms under the conditions of 300 DEG C -350 DEG C.
Further, the mantoquita is Salzburg vitriol and/or Gerhardite.
Further, the manganese salt is Manganous sulfate monohydrate and/or four nitric hydrate manganese.
Another is designed to provide a kind of dry method solid desulphurization denitration desulfurization denitrification agent to the purpose of the present invention, described
Desulfurization denitrification agent includes the catalyst of alkaline matter and above method preparation.
Further, the mass ratio of the alkaline matter and catalyst is 100:(0.2-8.0).
Further, the alkaline matter be magnesia, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide and/or
Calcium carbonate.
Third object of the present invention is to provide a kind of preparation method of dry method solid desulphurization denitration desulfurization denitrification agent,
The preparation method comprises the following steps that mass ratio, which is accounted for 100.0 parts, containing alkaline matter, mass ratio accounts for 0.2-
The water of 8.0 parts of catalyst and 0~20 mass ratio is after mediating, squeezing out and prepare bar, under the conditions of 50~100 DEG C,
It is obtained by drying in 0.5~2.0 hour.
The beneficial effects of the present invention are: 1, using by copper-manganese catalyst it is added to containing alkali metal and/or alkaline earth gold
In the carrier for belonging to component, the desulphurization denitration purpose under complicated flue gas condition is realized, avoid relying on accurate adjusting nitrogenous reducing agent
(NH3Or urea) caused by equipment and operating condition complexity；2, desulfurization denitrification agent transport provided by the invention, storage, replacement
It is convenient；3, catalyst provided by the invention is properly added in alkaline base-material, can play desulfurization and denitration, and
Existing technology is compared, and in the premise of identical desulfurization denitrification agent usage amount, technology provided by the invention can greatly improve desulfurization
Denitration ability.
Specific embodiment
Of the invention is using the oxygen containing compound of copper-manganese, mixture as catalyst, to contain alkali metal or alkaline-earth metal
The alkali compounds or mixture of component are the desulfurization denitrification agent of matrix.The range that the present invention is protected is not limited to be implemented as follows
Example.Basic principle according to the present invention, the engineer of this field the cleanser of attainable desulfurization off sulfide effect also belong to this
The protection scope of invention.
Embodiment 1
The Gerhardite and 48.0 4 nitric hydrate manganese for being 15.0 by mass parts, the KMnO that mass parts are 20.04, matter
The mass percent concentration that amount part is 100.0 parts is that 20.0% sodium carbonate liquor is distributed in the water that mass parts are 1000.0 and is formed
Slurry continues to be kept stirring 5 hours, and product is filtered, and washs, dry, after grinding, in air atmosphere, under the conditions of 300 DEG C
7 hours of calcination obtain catalyst a.
The calcium hydroxide for being 50.0 by mass parts, the calcium carbonate that mass parts are 50.0；The catalyst a that mass parts are 4.0；Matter
By mediating 10 minutes, squeezing out and prepare bar, bar dried under the conditions of 50 DEG C by 2.0 hours the water that amount part is 15
It is dry, obtain desulfurization denitrification agent A-1.
Control group A -2 is that the mass parts that catalyst a is added are 8.0, but the relative composition of carrier and gross mass part and A-1 phase
Together, production method is identical.
Control group A -3 is not add catalyst a, but the relative composition of carrier and gross mass part are identical as A-1, production method
It is identical.
The desulfurization off sulfide effect of A-1, A-2 and A-2 are listed in table 1.
Embodiment 2
By the Manganous sulfate monohydrate of the mass parts Salzburg vitriol for being 16.0 and mass parts 32.0, mass parts are 20.0
KMnO4, mass parts are that 100.0 parts of mass percent concentration is that be distributed to mass parts be 1000.0 to 20.0% sodium carbonate liquor
Slurry is formed in water, continues to be kept stirring 5 hours, product is filtered, and is washed, and it is dry, after grinding, in air atmosphere, in 350
5 hours of calcination under the conditions of DEG C obtain catalyst b.
The magnesium hydroxide for being 25.0 by mass parts, the magnesium carbonate that mass parts are 50.0, the calcium hydroxide that mass parts are 25.0；
The catalyst b that mass parts are 0.2, the water that mass parts are 20 is by mediating 10 minutes, squeezing out and prepare bar.Bar exists
Under the conditions of 100 DEG C, was dried by 2.0 hours, obtain desulfurization denitrification agent B-1.
Control group B-2 is that the mass parts that catalyst b is added are 3.0, but the relative composition of carrier and gross mass part and B-1 phase
Together, production method is identical.
Control group B-3 is not add catalyst b, but the relative composition of carrier and gross mass part are identical as B-1, production method
It is identical.
The desulfurization off sulfide effect of B-1, B-2 and B-2 are listed in table 1.
Embodiment 3
The Gerhardite for being 20.0 by mass parts, 5.0 Salzburg vitriol, the sulfuric acid monohydrate of mass parts 16.0
Manganese, four nitric hydrate manganese of mass parts 24.0, the KMnO that mass parts are 20.04, mass parts are that 150.0 parts of mass percent is dense
Degree is distributed in the water that mass parts are 1000.0 for 20.0% sodium carbonate liquor and forms slurry.Continue to be kept stirring 8 hours.Product
It is filtered, is washed, dry, after grinding, in air atmosphere, 5 hours of calcination under the conditions of 350 DEG C obtain catalyst c.
The calcium hydroxide for being 35.0 by mass parts, the magnesium hydroxide that mass parts are 15.0, the calcium carbonate that mass parts are 25.0,
The magnesia that mass parts are 25.0, the magnesia that mass parts are 25.0；The catalyst c that mass parts are 4.0, the water that mass parts are 20
By mediating 10 minutes, squeezing out and prepare bar.Bar dried by 1.5 hours under the conditions of 100 DEG C, obtains desulfurization
Denitrfying agent C-1.
Control group C-2 is that the mass parts that catalyst c is added are 6.0, but the relative composition of carrier and gross mass part and C-1 phase
Together, production method is identical.
Control group C-3 is not add catalyst c, but the relative composition of carrier and gross mass part are identical as C-1, production method
It is identical.
The desulfurization off sulfide effect of C-1, C-2 and C-2 are listed in table 1.
Embodiment 4
The Salzburg vitriol for being 160.0 by mass parts, the Manganous sulfate monohydrate of mass parts 32.0, mass parts are 20.0
KMnO4, mass parts are that 400.0 parts of mass percent concentration is that be distributed to mass parts be 1000.0 to 20.0% sodium carbonate liquor
Slurry is formed in water.Continue to be kept stirring 12 hours.Product is filtered, and is washed, dry, after grinding, in air atmosphere, in
5 hours of calcination under the conditions of 350 DEG C obtain catalyst d.
The calcium hydroxide for being 90.0 by mass parts, the calcium carbonate that mass parts are 10.0；The catalyst d that mass parts are 4.0, matter
The water that amount part is 15 is by mediating 10 minutes, squeezing out and prepare bar.Bar dried under the conditions of 100 DEG C by 1.0 hours
It is dry, obtain desulfurization denitrification agent D-1.
Control group D-2 is that the mass parts that catalyst d is added are 8.0, but the relative composition of carrier and gross mass part and D-1 phase
Together, production method is identical.
Control group D-3 is not add catalyst d, but the relative composition of carrier and gross mass part are identical as D-1, production method
It is identical.
The desulfurization off sulfide effect of D-1, D-2 and D-3 are listed in table 1.
Embodiment 5
The Salzburg vitriol for being 396.0 by mass parts, the Manganous sulfate monohydrate of mass parts 32.0, mass parts are 20.0
KMnO4, mass parts are that 900.0 parts of mass percent concentration is that be distributed to mass parts be 1000.0 to 20.0% sodium carbonate liquor
Slurry is formed in water.Continue to be kept stirring 24 hours.Product is filtered, and is washed, dry, after grinding, in air atmosphere, in
8 hours of calcination under the conditions of 300 DEG C obtain catalyst e.
The calcium hydroxide for being 100.0 by mass parts；The catalyst d that mass parts are 5.6, the water that mass parts are 10 is by mediating
10 minutes, squeeze out prepare bar.Bar dried by 0.5 hour under the conditions of 80 DEG C, obtains desulfurization denitrification agent E-1.
Control group E-2 is that the mass parts that catalyst e is added are 8.4, but the relative composition of carrier and gross mass part and E-1 phase
Together, production method is identical.
Control group E-3 is not add catalyst e, but the relative composition of carrier and gross mass part are identical as E-1, production method
It is identical.
The desulfurization off sulfide effect of E-1, E-2 and E-3 are listed in table 1.
Embodiment 6
The Gerhardite for being 192.0 by mass parts, 198.0 Salzburg vitriol, four hydrations of mass parts 48.0
Manganese nitrate, the KMnO that mass parts are 20.04, mass parts are that 900.0 parts of mass percent concentration is 20.0% sodium carbonate liquor
It is distributed in the water that mass parts are 1000.0 and forms slurry.Continue to be kept stirring 24 hours.Product is filtered, and is washed, dry, is ground
After mill, in air atmosphere, 8 hours of calcination under the conditions of 325 DEG C obtain catalyst f.
The magnesium hydroxide for being 10.0 by mass parts, the magnesium carbonate that mass parts are 5.0, the calcium hydroxide that mass parts are 85.0；
The catalyst f that mass parts are 3.5, the water that mass parts are 15 is by mediating 10 minutes, squeezing out and prepare bar.Bar is 75
Under the conditions of DEG C, was dried by 2.0 hours, obtain desulfurization denitrification agent F-1.
Control group F-2 is that the mass parts that catalyst f is added are 6.3, but the relative composition of carrier and gross mass part and F-1 phase
Together, production method is identical.
Control group F-3 is not add catalyst f, but the relative composition of carrier and gross mass part are identical as F-1, production method
It is identical.
The desulfurization off sulfide effect of F-1, F-2 and F-3 are listed in table 1.
Control group 1
The calcium hydroxide for being 95.0 by mass parts, the sodium hypochlorite that mass parts are 5.0, the water that mass parts are 50.0 pass through
60 minutes are mediated, squeezes out and prepares bar.Bar dried by 2.0 hours under the conditions of 100 DEG C, obtains desulphurization denitration
Agent G-1.The desulfurization off sulfide effect of G-1 is listed in table 1.
Control group 2
The calcium carbonate for being 95.0 by mass parts, the NaClO that mass parts are 5.0, the water that mass parts are 50.0, by mediating 60
Minute squeezes out and prepares bar.Bar dried by 2.0 hours under the conditions of 60 DEG C, obtains desulfurization denitrification agent H-1.H-
1 desulfurization off sulfide effect is listed in table 1.
Control group 3
The magnesium hydroxide for being 85.0 by mass parts, the kaolin that mass parts are 5.0, the KMnO that mass parts are 4.04, quality
The Aluminum sol that part is 6.0 is (according to Al2O3Mass percentage is the 20%) water that mass parts are 75.2, by mediating 60 minutes
To powder, under the conditions of 80 DEG C, was dried by 1.0 hours, obtain desulfurization denitrification agent I-1.Because product can not form, do not survey de-
Sulphur denitration performance.
Control group 4
The magnesium carbonate for being 85.0 by mass parts, the kaolin that mass parts are 5.0, the KMnO that mass parts are 4.04, mass parts
For 6.0 Aluminum sol (according to Al2O3Mass percentage is that 20%), the water that mass parts are 75.2 is obtained by mediating 60 minutes
Powder.Bar dried by 1.0 hours under the conditions of 80 DEG C, obtains desulfurization denitrification agent J-1.The desulfurization off sulfide effect of J-1
It is listed in table 1.
Control group 5
The sodium bicarbonate for being 90.0 by mass parts, the KMnO that mass parts are 1.04, mass parts be 1.0 CeO2, mass parts are
8.0 Aluminum sol is (according to Al2O3Mass percentage is the 20%) water that mass parts are 73.6, by mediating 60 minutes, squeezing out
Prepare bar.Bar dried by 1.0 hours under the conditions of 80 DEG C, obtains desulfurization denitrification agent K-1.The desulfurization of K-1 is de-
Nitre effect is listed in table 1.
Control group 6
The calcium hydroxide for being 60.0 by mass parts, the diatomite that mass parts are 5.0, the KMnO that mass parts are 34.54, quality
The CeO that part is 0.52, the water that mass parts are 80.0, by mediating 60 minutes, squeezing out and prepare bar.Bar is in 80 DEG C of items
Under part, was dried by 1.0 hours, obtain desulfurization denitrification agent L-1.The desulfurization off sulfide effect of L-1 is listed in table 1.
Control group 7
The calcium hydroxide for being 60.0 by mass parts, the diatomite that mass parts are 5.0, the KMnO that mass parts are 33.54, quality
The CeO that part is 0.52, mass parts be 1.0 SiO2, the water that mass parts are 80.0, by mediating 60 minutes, squeezing out and prepare strip
Object.Bar dried by 1.0 hours under the conditions of 80 DEG C, obtains desulfurization denitrification agent M-1.The desulfurization off sulfide effect of M-1 is listed in
Table 1.
Control group 8
By mass parts be 89.0 magnesium hydroxide, mass parts be 5.0 diatomite, mass parts be 6.0 Aluminum sol (according to
Al2O3Mass percentage is the 20%) water that mass parts are 75.2, powder is obtained by mediating 60 minutes, in 80 DEG C of conditions
Under, it was dried by 1.0 hours, obtains desulfurization denitrification agent N-1.Because product can not form, desulphurization denitration performance is not surveyed.
Control group 9
By mass parts be 89.0 magnesium carbonate, mass parts be 5.0 diatomite, mass parts be 6.0 Aluminum sol (according to
Al2O3Mass percentage is the 20%) water that mass parts are 75.2, by mediating 60 minutes, squeezing out and prepare bar.Strip
Object dried by 1.0 hours under the conditions of 80 DEG C, obtains desulfurization denitrification agent O-1.The desulfurization off sulfide effect of O-1 is listed in table 1.
Control group 10
The sodium bicarbonate for being 91.0 by mass parts, the CeO that mass parts are 5.02, mass parts be 8.0 Aluminum sol (according to
Al2O3Mass percentage is the 20%) water that mass parts are 76.8, by mediating 60 minutes, squeezing out and prepare bar.Strip
Object dried by 1.0 hours under the conditions of 80 DEG C, obtains desulfurization denitrification agent P-1.The desulfurization off sulfide effect of P-1 is listed in table 1.
Control group 11
The calcium hydroxide for being 94.5 by mass parts, the diatomite that mass parts are 5.0, the CeO that mass parts are 0.52, mass parts
For 80.0 water, by kneading 60 minutes, squeezes out and prepare bar.Bar dried under the conditions of 80 DEG C by 1.0 hours
It is dry, obtain desulfurization denitrification agent Q-1.The desulfurization off sulfide effect of Q-1 is listed in table 1.
Control group 12
The calcium hydroxide for being 93.5 by mass parts, the diatomite that mass parts are 5.0, the CeO that mass parts are 0.52, mass parts
For 1.0 SiO2, the water that mass parts are 80.0, by mediating 60 minutes, squeezing out and prepare bar.Bar is in 80 DEG C of conditions
Under, it was dried by 1.0 hours, obtains desulfurization denitrification agent R-1.The desulfurization off sulfide effect of R-1 is listed in table 1.
Denitration performance test mode:
1. by 8.0g desulfurization denitrification agent sample as in quartz ampoule, and quartz ampoule is preheated in specified temperature, temperature
Spending setting value is 110 DEG C.
2. following four kinds typical hybrid analog-digital simulation flue gases are used, after preheating under the conditions of 110 DEG C of temperature, with 2600h-1Sky
Speed is passed through in above-mentioned quartz ampoule, specific smoke test composition and concentration are as follows: SO2(200ppm), NO (300ppm), H2O
(2.5%), O2(5.0%) carrier gas is N2Gas；
3. the calculation formula of desulfurization or denitration process ability (unit: milligram/cubic meter) and being described as follows:
Desulfurization denitrification agent removes the SO in simulated flue gas or practical flue gas in 60 minutes2Or the quality of NO；
Pass through the simulated flue gas of desulfurization denitrification agent or the operating condition volume in practical flue gas in 60 minutes.
Because must satisfy environmental requirement in view of processing flue gas practical capacity and efficiency.For this reason, it may be necessary in fume treatment energy
Power replaces desulfurization denitrification agent before reaching capacity.Accordingly, it is considered to the dry desulfurization denitrfying agent of current document and this
The actual effect for inventing the desulfurization nitre agent of protection, determining 60 minutes has as the desulphurization and denitration ability for investigating desulfurization denitrification agent
Operability.
Using the above method to the desulfurization denitrification agent of Examples 1 to 6 and control group 1-12 to the desulfurization process of simulated flue gas
Ability denitration process ability (milligram/cubic meter), as a result as shown in the table:
Seen from table 1, the denitration ability of K-1, M-1 and L-1 is not with the KMnO in desulfurization denitrification agent4Amount increase and it is bright
It is aobvious to increase, and G-1 and H-1 addition NaClO, K-1, L-1, M-1, P-1, Q-1 and R-1 add CeO2Two kinds of addition situations
Denitration ability is had no significant effect.Therefore, from the point of view of experimental conditions, with calcic and/or the alkaline base-material of magnesium, strong oxidizer is added
Come the method for processing capacity that improves denitration, there are limitations.The catalysis in desulfurization denitrification agent that the present invention protects by taking B-2 as an example
Agent can be in 3.0% additive amount, it will be apparent that by the denitration ability of B-3 control sample by 0mg/m3It is increased to 48mg/
m3.And it is apparently higher than K-1, the 34mg/m of M-1 and L-13-36mg/m3Denitration ability.In addition, with alkaline base-material and addition catalysis
From the point of view of the case where agent or oxidant, desulfurization effect is obvious.
To sum up, the catalyst that the present invention protects is properly added in alkaline base-material, can play desulfurization and denitration
Effect.This product is suitble to use in the case where dry desulfurization and/or denitration, also, transport, storage, replacement desulfurization denitrification agent compared with
For convenience.
Claims (10)
1. a kind of dry method solid desulphurization denitration catalyst, which is characterized in that the catalyst be containing mantoquita and/or manganese salt,
It is formed after potassium permanganate and sodium carbonate mixing in calcination.
2. a kind of dry method solid desulphurization denitration catalyst as described in claim 1, which is characterized in that the catalyst
The preparation method is as follows: more than one mass ratio to be accounted for 15.0-396.0 parts of mantoquita and/or more than one mass ratio
Account for 32.0-48.0 parts of manganese salt, mass ratio accounts for 10.0-30 parts of KMnO4And mass ratio accounts for 100.0-900.0 parts of carbon
Acid sodium solution, which is distributed in solvent, forms slurry, stirring, after product is filtered, washed, is dried, being ground, in air atmosphere, in
Calcination forms under the conditions of 300 DEG C -350 DEG C.
3. a kind of dry method solid desulphurization denitration catalyst as claimed in claim 2, which is characterized in that the solvent is
Water, the mass ratio of the water account for 1000.0 parts.
4. a kind of dry method solid desulphurization denitration catalyst as described in claim 1, which is characterized in that the mantoquita is five
Hydrated copper sulfate and/or Gerhardite.
5. a kind of dry method solid desulphurization denitration catalyst as described in claim 1, which is characterized in that the manganese salt is one
Hydrated manganese sulfate and/or four nitric hydrate manganese.
6. a kind of dry method solid desulphurization denitration desulfurization denitrification agent, which is characterized in that the desulfurization denitrification agent includes alkalinity
Substance, and the dry method solid desulphurization denitration catalyst as described in claim 1-5 any claim.
7. a kind of dry method solid desulphurization denitration desulfurization denitrification agent as claimed in claim 6, which is characterized in that the alkalinity
The mass ratio of substance and catalyst is 100:(0.2-8.0).
8. a kind of dry method solid desulphurization denitration desulfurization denitrification agent as claimed in claim 7, which is characterized in that the alkalinity
Substance is magnesia, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide and/or calcium carbonate.
9. a kind of preparation method of dry method solid desulphurization denitration desulfurization denitrification agent, which is characterized in that the preparation method packet
It includes following step: mass ratio is wanted for 100.0:(0.2-8.0) containing alkaline matter and such as any right of claim 1-5
The dry method solid desulphurization denitration catalyst is sought, adds water after mediating, squeezing out, under the conditions of 50~100 DEG C, is passed through
Drying in 0.5~2.0 hour obtains.
10. a kind of preparation method of dry method solid desulphurization denitration desulfurization denitrification agent as claimed in claim 9, feature exist
In the shape of extrudate is strip.
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| CN111871397A (en) * | 2020-08-05 | 2020-11-03 | 浙江澄宇环保新材料股份有限公司 | Desulfurizing agent for steelmaking and production process thereof |
| CN112337426A (en) * | 2020-06-05 | 2021-02-09 | 河南众仕联环境工程有限公司 | Adsorbent capable of being used for low-temperature dry desulfurization and denitrification in steel mill and preparation method thereof |
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| CN116099351A (en) * | 2022-12-29 | 2023-05-12 | 杭州尚善若水环保科技有限公司 | Desulfurization agent and desulfurization method for garbage incineration flue gas treatment |
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