CN110124478A - It is suitable for the denitration material and its method of denitration of cement kiln using nickel slag as raw material preparation - Google Patents
It is suitable for the denitration material and its method of denitration of cement kiln using nickel slag as raw material preparation Download PDFInfo
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- CN110124478A CN110124478A CN201910522084.8A CN201910522084A CN110124478A CN 110124478 A CN110124478 A CN 110124478A CN 201910522084 A CN201910522084 A CN 201910522084A CN 110124478 A CN110124478 A CN 110124478A
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- denitration
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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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
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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
- B01D53/81—Solid phase processes
- B01D53/83—Solid phase processes with moving reactants
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A kind of denitration material and its method of denitration being suitable for cement kiln using nickel slag as raw material preparation, belongs to industrial furnace smoke denitration field.Using nickel slag as raw material, using acid dissolution, alkali is added dropwise, and porous denitration material is made in the method for adjusting pH precipitating.This preparation method uses industrial residue for raw material, save the cost, simple process, really realizes the resource utilization of waste residue.This denitration material is higher up to 80% or more in high-temperature region (700 DEG C~1000 DEG C) denitrification rate.This porous material is uniformly mixed with cement slurry with certain mass ratio, when the mass ratio shared by the porous material is 5%, denitrification rate is up to 90% or more in 700 DEG C~1000 DEG C temperature ranges.The present invention realizes that industrial residue recycles, and turns waste into wealth, and protects environment；Without using reducing agents such as ammonium hydroxide or urea in denitrification process, the security risk and the escaping of ammonia secondary pollution problems in reducing agent storage and transport process are eliminated；Denitration material obtained is injected directly into cement kiln with cement slurry, it is not necessary that redundant equipment is reequiped or increased to kiln.
Description
Technical field
The present invention relates to a kind of combination cement production process, the method for removing denitrification using industrial residue is specifically related to
And a kind of denitration material and its method of denitration being applicable in cement kiln using the preparation of nickel slag, it is de- to belong to industrial furnace smoke
Nitre processing technology field.
Background technique
Nitrogen oxides (NOx) has directly human health, the ecosystem and building facility as one of atmosphere pollution
With it is potentially hazardous.The main source of NOx is the burning of fossil fuel, mainly includes motor-vehicle tail-gas, industrial production generation
Nitrogen oxides etc..The discharge amount of cement kiln nitrogen oxides is only second to thermal power plant and motor-vehicle tail-gas, becomes the third-largest pollution sources.
Currently, the cement kiln denitration technology of comparative maturity has low nitrogen burning control technology, SCR technology (SCR) and choosing
Selecting property non-catalytic reduction technology (SNCR).Cost is relatively low for low-NO_x combustion technology, but denitration efficiency is low, is usually no more than 30%, nothing
Method reaches the discharge standard of country.SNCR denitration technology is to utilize NH3, urea etc. make reducing agent, in 800~1000 DEG C with
NOx reaction generates N2.Denitration efficiency is low, and generally 30%~50%, and liquefied ammonia consumption is larger (ammonia nitrogen is than about 1.6).SCR
Denitration technology refers under the effect of the catalyst, utilizes reducing agent (such as NH3, urea) reacted with NOx generate N2And H2O.Currently
The price of SCR catalyst is higher, and catalyst poisoning easily occurs in performance less stable, causes the service life of catalyst short.And
Both denitration technologies of SCR and SNCR require to use ammonia or urea as reducing agent, need to store up ammonia (urea) and spray ammonia (urine
Element) device, it takes up a large area, reaction unit is complicated, and cost of investment and operating cost are high, thereby increases and it is possible to it will appear the escaping of ammonia phenomenon,
Cause secondary pollution.Therefore, selection is at low cost, without using the denitration of the reducing agents such as ammonia or urea and denitrification rate with higher
Material is of great significance.
Nickel slag is to be formed by during smelting nickel with FeO, SiO2Fusant as main component is formed after water quenching
Granulated slag, be one of maximum industrial residue of discharge amount.According to China's nickel production technology, every production 1t nickel is about discharged 6~
16t nickel slag.It is all that stockpiling is idle in the disposal options at present to nickel slag, due to cannot rationally utilize for a long time, country's stockpiling
Nickel slag has reached 40,000,000 tons, also about 2,000,000 tons newly-increased every year.The idle not only land occupation of stockpiling, causes sternly surrounding enviroment
Heavily contaminated, and high risks are caused to human health, and valuable component cannot also recycle in nickel slag.Therefore, locating
Retentive activity component Fe as far as possible when managing nickel slag removes impurity element Ca, Mg etc., makes it have preferable denitration, saves
While cost, the resource utilization to nickel slag is also realized.
The present invention is directed to be raw material using nickel slag, a kind of denitration material of high-specific surface area is prepared, and combine manufacture of cement
This denitration material is injected directly into cement kiln by technique, as material enters in preheater and dore furnace, is not using ammonia
Or when the reducing agents such as urea, with the raising of kiln in-furnace temperature, reach the method for higher denitrification rate.
Summary of the invention
In view of the above problems, the present invention develops a kind of suitable inorganic porous material of cement kiln denitration by raw material of nickel slag
Material reaches the method for higher denitrification rate in conjunction with cement production process under without using reducing agents such as ammonium hydroxide or urea.
(1) it is suitable for the method for the denitration material of cement kiln using nickel slag as raw material preparation, which is characterized in that including following
Step:
Porous denitration material is prepared by raw material of nickel slag, 2h is mixed in the hydrochloric acid solution behind nickel ground-slag end and dilution,
Nickel ground-slag end and hydrochloric acid solution mixed proportion are that 10g nickel ground-slag end is mixed in the dilute hydrochloric acid that 60mL concentration is 3mol/L；It is added
After sodium hydroxide aqueous slkali adjusting pH is 3~11,30min is stirred；More than three times, the sediment isolated is placed in for centrifuge washing
Dry 12h, is made porous denitration material in 80 DEG C of drying boxes.
Further, the concentration of sodium hydroxide solution is 2mol/L.
It (2) is 1000ppmNO, N in flue gas condition2For Balance Air, gas flow rate 300ml/min, temperature condition is 25
DEG C~1000 DEG C when denitration.The porous denitration material of preparation is placed in denitration test device and tests its denitration effect by method of denitration
Rate.With N2For Balance Air, catalyst amount 2mL, flue gas group becomes ω (NO)=1000ppm, is warming up at 25 DEG C of room temperature
1000 DEG C, in the ingredient and content of different temperature points measurement exiting flue gas, the variation for varying with temperature denitrification rate is calculated, thus
The denitration performance for symbolizing porous material, in high-temperature temperature region, the denitrification rate of 700 DEG C~1000 DEG C of porous materials is higher, substantially
Reach 80% or more, reaches as high as 99.8%.
(3) the porous denitration material prepared using nickel slag is mixed in varing proportions with cement slurry, is tried after test mixing
Denitration efficiency of the sample at 700 DEG C~1000 DEG C of high-temperature is measuring denitration when the mass ratio shared by the porous material is 1%~5%
Rate is still up to 80% or more.It is 3%-5% that wherein denitration material, which accounts for mixture quality ratio, in 700 DEG C~1000 DEG C temperature ranges
Denitration is higher.
Advantages of the present invention are as follows: first is that use the nickel slag of one of industrial residue for raw material, using being simply chemically treated
To the porous denitration material of high-specific surface area, industrial residue is recycled, and really realizing turns waste into wealth.Second is that the present invention does not use ammonia
The reducing agents such as water or urea avoid security risk and secondary pollution problem in the reducing agents storage and transport process such as ammonium hydroxide or urea；
Cement slurry is mixed with prepared porous material and is sprayed into cement kiln by the present invention simultaneously, without increasing extra device,
It is easy to operate and cost is relatively low without to existing kiln transformation.And the porous denitration material using the preparation of nickel slag is determined 25
DEG C~1000 DEG C of temperature under the conditions of denitration efficiency show it is higher in the denitrification rate of the 700 DEG C~1000 DEG C of porous materials in high-temperature region,
80% or more is basically reached, reaches as high as 99.8%.
Detailed description of the invention
Fig. 1 is the denitrification rate of section Example 1 of the present invention, embodiment 2 and embodiment 3
Specific embodiment
Below with reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
The nickel ground-slag end 10g is mixed with the hydrochloric acid solution that 60ml concentration is 3mol/L, after 2h is stirred at room temperature, in lasting stirring
In, the NaOH solution of 2mol/L is added dropwise, adjusting pH is 3, stirs 30min；It is centrifugated out bottom precipitation, after washing 3 times, 80 DEG C
Dry 12h, is made denitration material powder.Simulated flue gas ingredient 1000ppmNO, N2For Balance Air, gas flow rate 300ml/
Min tests denitration efficiency within the temperature range of 25 DEG C~1000 DEG C, increases denitrification rate with temperature and increases, 700 DEG C of high-temperature region
~1000 DEG C of denitrification rates are higher substantially 85%, and highest denitrification rate is 98.3%, and denitrification rate varies with temperature curve and sees Fig. 1 (b).
Embodiment 2
The nickel ground-slag end 10g is mixed with the hydrochloric acid solution that 60ml concentration is 3mol/L, after 2h is stirred at room temperature, in lasting stirring
In, the NaOH solution of 2mol/L is added dropwise, adjusting pH is 7, stirs 30min；It is centrifugated out bottom precipitation, after washing 3 times, 80 DEG C
Dry 12h, is made denitration material powder.Simulated flue gas ingredient 1000ppmNO, N2For Balance Air, gas flow rate 300ml/
Min tests denitration efficiency within the temperature range of 25 DEG C~1000 DEG C, and 700 DEG C~1000 DEG C of high-temperature region, denitrification rate is compared with Gao Ji
This is 95%, and highest denitrification rate is 99.8%, and denitrification rate varies with temperature curve and sees Fig. 1 (b).
Embodiment 3
The nickel ground-slag end 10g is mixed with the hydrochloric acid solution that 60ml concentration is 3mol/L, after 2h is stirred at room temperature, in lasting stirring
In, the NaOH solution of 2mol/L is added dropwise, adjusting pH is 11, stirs 30min；It is centrifugated out bottom precipitation, after washing 3 times, 80
DEG C dry 12h, is made denitration material powder.Simulated flue gas ingredient 1000ppmNO, N2For Balance Air, gas flow rate 300ml/
Min tests denitration efficiency within the temperature range of 25 DEG C~1000 DEG C, is 85% in 800 DEG C~1000 DEG C of high-temperature region denitrification rate,
Highest denitrification rate is 99.4%, and denitrification rate varies with temperature curve and sees Fig. 1 (c).
Embodiment 4
Preparing for denitration material is as described in Example 2, by the denitration material of preparation and cement slurry according to certain quality
Than mixing, porous material and cement slurry mixed proportion are 3%:97%, are ground porous material and cement slurry using mortar
After uniformly, 2mL composite sample is fitted into denitrification test pipe.It is 1000ppmNO, N in flue gas condition2For Balance Air, gas stream
Speed is 300ml/min, and denitration temperature is 700~1000 DEG C, after being mixed using denitration device test porous material with cement slurry
Denitrification rate be essentially 60% or more (such as table 1).
Embodiment 5
Preparing for denitration material is as described in Example 2, by the denitration material of preparation and cement slurry according to certain quality
Than mixing, porous material and cement slurry mixed proportion are 5%:95%, are ground porous material and cement slurry using mortar
After uniformly, 2mL composite sample is fitted into denitrification test pipe.It is 1000ppmNO, N in flue gas condition2For Balance Air, gas stream
Speed is 300ml/min, and denitration temperature is 700~1000 DEG C, after being mixed using denitration device test porous material with cement slurry
Denitrification rate it is still higher, be maintained at 90% or more (such as table 1).
Denitrification rate/% of table 1. embodiment 4 and embodiment 5
| 700℃ | 800℃ | 900℃ | 1000℃ | |
| Embodiment 4 | 64.83 | 81.02 | 92.45 | 96.63 |
| Embodiment 5 | 93.76 | 95.34 | 97.82 | 96.95 |
Claims (4)
1. being suitable for the method for the denitration material of cement kiln using nickel slag as raw material preparation, which comprises the following steps:
Porous denitration material is prepared by raw material of nickel slag, 2h, nickel slag is mixed in the hydrochloric acid solution behind nickel ground-slag end and dilution
Powder and hydrochloric acid solution mixed proportion are that 10g nickel ground-slag end is mixed in the dilute hydrochloric acid that 60mL concentration is 3mol/L；Hydrogen-oxygen is added
After change soda solution adjusting pH is 3~11,30min is stirred；Centrifuge washing is placed in 80 DEG C more than three times, by the sediment isolated
Dry 12h, is made porous denitration material in drying box.
2. method according to claim 1, which is characterized in that the concentration of sodium hydroxide solution is 2mol/L.
3. the application of the denitration material of method preparation as described in claim 1, which is characterized in that be in flue gas condition
1000ppmNO, N2For Balance Air, gas flow rate 300ml/min, denitration when temperature condition is 25 DEG C~1000 DEG C.
4. application as claimed in claim 3, which is characterized in that in flue gas condition be 1000ppmNO, N2For Balance Air, gas stream
Speed is 300ml/min, this denitration material is uniformly mixed with different quality ratio with cement slurry, wherein denitration material accounts for mixture
Mass ratio is 3%-5%, the denitration in 700 DEG C~1000 DEG C temperature ranges.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910522084.8A CN110124478B (en) | 2019-06-17 | 2019-06-17 | Denitration material prepared from nickel slag and suitable for cement kiln and denitration method thereof |
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| CN201910522084.8A CN110124478B (en) | 2019-06-17 | 2019-06-17 | Denitration material prepared from nickel slag and suitable for cement kiln and denitration method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112452144A (en) * | 2020-11-05 | 2021-03-09 | 北京工业大学 | Method for preparing denitration material for cement preheater from gasified slag |
| CN112495153A (en) * | 2020-11-05 | 2021-03-16 | 北京工业大学 | Method for preparing cement kiln denitration porous material by using household garbage incineration fly ash |
| CN112495446A (en) * | 2020-12-17 | 2021-03-16 | 南京永能新材料有限公司 | Cement denitration catalyst and preparation method and application thereof |
| CN112933954A (en) * | 2021-01-15 | 2021-06-11 | 安徽萃智环保科技有限公司 | Cement kiln semi-dry SCR denitration system and method |
| CN116116422A (en) * | 2023-02-03 | 2023-05-16 | 山东博然电力科技有限公司 | Preparation process and application of flue gas denitration catalyst |
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| CN116116422B (en) * | 2023-02-03 | 2023-06-20 | 山东博然电力科技有限公司 | Preparation process and application of flue gas denitration catalyst |
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