CN110496610A - A kind of regenerative agent and regeneration method for desulphurization denitration waste active carbon - Google Patents
A kind of regenerative agent and regeneration method for desulphurization denitration waste active carbon Download PDFInfo
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- CN110496610A CN110496610A CN201910804579.XA CN201910804579A CN110496610A CN 110496610 A CN110496610 A CN 110496610A CN 201910804579 A CN201910804579 A CN 201910804579A CN 110496610 A CN110496610 A CN 110496610A
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- active carbon
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- desulphurization denitration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
Abstract
The present invention discloses a kind of regenerative agent and regeneration method for desulphurization denitration waste active carbon, spray phase is added on existing active carbon hot recycling Process ba- sis, regenerative agent is uniformly sprayed on to waste active carbon and in the sectional temperature-controlled activation of high temperature furnace, be directly loadable into equipment of the regenerated carbon after the completion of activating by washing, drying reuses.Regenerative agent is made of activator, activator promotor, stabilizer and water.That the present invention provides formulas is simple, works well, and cost is relatively low and application method is simply to the regeneration method of desulphurization denitration waste active carbon, can be obviously shortened activity time and restore or the absorption property of enhancing active carbon.
Description
Technical field
The invention belongs to sintering gas purifying process fields, refer primarily to a kind of regeneration for desulphurization denitration waste active carbon
Agent and regeneration method.
Background technique
Sintering is a complicated physical and chemical process, and the flue gas discharged has low temperature, complicated component, discharge amount big etc.
Feature, wherein SO2Discharge amount accounts for 60% or more of iron and steel enterprise's total release, additionally contains NOx, other pollutions such as heavy metal
Object.Therefore, sintering is that more serious one of process is polluted in steel manufacture process.Active carbon is a kind of carbon with porous structure
Material, due to its large specific surface area, internal pore structure is flourishing, so that active carbon is had excellent absorption property, is widely used
In catalysis, absorption, energy reserves and medicine and other fields.
With the continuous increase of the usage amount of active carbon, the yield of waste active carbon also continues to increase.What is largely generated is useless
Active carbon not only pollutes environment, but also be also the wasting of resources without recycling.Currently, the regeneration method master of useless activated carbon
If hot recycling method, i.e., waste active carbon is handled by the method for heating, make the organic matter being tightly held by activated carbon under the high temperature conditions
Charing is decomposed, and gaseous material evolution is converted to, thus the absorption property of activity recovery charcoal.Majority iron and steel enterprise is for being sintered now
The active carbon of flue gas desulfurization and denitrification uses thermal regeneration method.However, hot recycling equipment operation energy consumption is high, the loss late of charcoal is higher,
The problems such as active carbon mechanical strength after regeneration is low solves there is still a need for further.Chinese patent literature CN106345440A is provided
A kind of method of regenerated carbon washs activator with deionized water and keeps the temperature a few hours in oxidizing atmosphere, but it is deposited
In following problems: regenerated carbon adsorption effect is bad, and mechanical strength reduces etc., is unfavorable for waste active carbon recycling.It is Chinese special
Sharp document CN106378120A provides a kind of regenerating active carbon system and regeneration method, and this method is cumbersome and regenerates temperature
Degree is high, the reproduction time is long, therefore this method is not suitable for industrially applying on a large scale.
Summary of the invention
The purpose of the present invention is to provide a kind of regenerative agents and regeneration method for desulphurization denitration waste active carbon, to solve
In the prior art, the bad defect of adsorption effect after regenerating active carbon.
The present invention adopts the following technical scheme:
A kind of regenerative agent for desulphurization denitration waste active carbon, is calculated in mass percent, comprising:
5%~10% activator, 2%~4% activator promotor, the stabilizer of 1%-3%, remaining is water.
Activator is NaOH, KOH and K2CO3One or more of mixtures.
Activator promotor is FeSO4With CuSO4One or two kinds of mixtures.
Stabilizer is Mg (NO3)2With Ba (NO3)2One or two kinds of mixtures.
A kind of regeneration method for desulphurization denitration waste active carbon, comprises the following processes:
The regenerative agent for being used for desulphurization denitration waste active carbon is uniformly sprayed on and is used for desulphurization denitration waste active carbon, then into
It goes and is activated, be activated and use temperature-gradient method, temperature-gradient method is divided into drying, decomposition and activation three phases, from decomposition rank
Section starts, and is purged and is activated to for desulphurization denitration waste active carbon using vapor, realizes for the useless activity of desulphurization denitration
The regeneration of charcoal.
The fountain height of regenerative agent for desulphurization denitration waste active carbon are as follows:
It is per ton that the regenerative agent that desulphurization denitration waste active carbon is used for described in 50~80kg is sprayed for desulphurization denitration waste active carbon.
When drying, temperature control is at 180 DEG C~250 DEG C, time 15-30min.
When decomposition, temperature control is at 450 DEG C~550 DEG C, time 20-30min.
When activation, temperature control is at 750 DEG C~800 DEG C, time 40-60min.
Vapor is (2:1)~(4:1) with the mass ratio for desulphurization denitration waste active carbon.
The invention has the following beneficial effects:
In regenerative agent for desulphurization denitration waste active carbon of the invention, activator can be for the useless activity of desulphurization denitration
In charcoal regenerative process, struts fragrant synusia and bring it about distortion or deformation, create new hole；Stabilizer can further aoxidize
The charcoal of formation, plays further oxidation, corrodes charcoal body and pore-creating, forms the microstructure of micropore prosperity；Activator promotor energy
The reaction activity of carbon water reaction is reduced, the progress of carbon water reaction is promoted.These three additions of activator, activator promotor and stabilizer
Agent can be cooperateed with mutually and be played a role, and can not only accelerate the process of regenerating active carbon, but also can enhance single regenerative agent
Regeneration effect.Therefore it is able to use using regenerative agent of the invention in the regeneration of desulphurization denitration waste active carbon.
The present invention is in the regeneration method of desulphurization denitration waste active carbon, drying stage to be useless for desulphurization denitration for removing
Moisture in active carbon；Catabolic phase is used to decompose the organic matter for the absorption of desulphurization denitration waste active carbon and is blocked in hole
Inorganic salts；Activation stage is used to restore the porous structure and adsorption capacity of waste active carbon.Heating is conducive to desorb stage by stage
Active carbon hole is discharged in product in time, while being also beneficial to regenerative agent and enter hole preferably to play a role.When regeneration, it will use
It is uniformly sprayed in the regenerative agent of desulphurization denitration waste active carbon for desulphurization denitration waste active carbon, it is easy to operate, it does not need again
Configure dedicated activation equipment.Regeneration method through the invention, the methylene blue adsorption value of gained active carbon is 181~
189mg/g, iodine sorption value are 1335.8~1388.34mg/g, and Penetrating curve is 70wt.%~74wt.%.Therefore it adopts
With the regeneration method for desulphurization denitration waste active carbon of the invention, it is capable of the waste active carbon of effective regeneration adsorption saturation, even
Further increase the absorption property of active carbon.
Specific embodiment
Below by way of example, the invention will be further described:
In view of the deficiencies of the prior art, the regeneration method for desulphurization denitration waste active carbon of the invention, scientific and reasonable, letter
It is single easy, shorten the waste active carbon hot recycling time, the energy consumption of hot recycling process, regeneration effect is good.Its process includes
Following steps:
1) it will be used for the screening of desulphurization denitration waste active carbon, it is useless for desulphurization denitration less than 3mm to remove powdered and granularity
Active carbon；
2) it is formulated for the regenerative agent of desulphurization denitration waste active carbon, the regenerative agent is by by activator, activator promotor and steady
Determine agent be dissolved in water be made；
3) regenerative agent made from step 2) is uniformly sprayed on for desulphurization denitration waste active carbon, then in high temperature furnace
High-temperature activation is carried out, the high-temperature activation stage uses temperature-gradient method, is divided into three drying, decomposition, activation temperature stages, and from second
Stage (i.e. catabolic phase) starts to be passed through vapor into high temperature furnace, and vapor is for purging and activating；
4) after the regenerated carbon that activation finishes is cooling, adsorption system use can be again loaded by washing, drying.
Wherein, it in the regenerative agent for desulphurization denitration waste active carbon, is calculated in mass percent, includes 5%~10%
Activator, 2%~4% activator promotor, 1%-3% stabilizer, surplus is water.
Activator component is NaOH, KOH and K2CO3One or more mixtures, activator promotor ingredient be FeSO4With
CuSO4One or two kinds of mixtures, stabilizer is Mg (NO3)2With Ba (NO3)2One or two kinds of mixtures, regenerative agent
Fountain height be 50~80kg/t.
First temperature section is drying stage, and temperature control is at 180 DEG C~250 DEG C, time 15-30min, second temperature section
For catabolic phase, at 450 DEG C~550 DEG C, time 20-30min, third temperature section is activation stage, temperature control for temperature control
System is at 750 DEG C~800 DEG C, time 40-60min.Since catabolic phase, using vapor to for the useless activity of desulphurization denitration
Charcoal is purged and is activated.
It is (2:1)~(4:1) that vapor, which is passed through, with the mass ratio for desulphurization denitration waste active carbon sieve.
Embodiment 1
The present embodiment is used for the regeneration method of desulphurization denitration waste active carbon, the steps include:
1) by certain steel plant's flue gas desulfurization and denitrification treated waste active carbon, waste active carbon screening removes powdered and grain
Degree is less than the waste active carbon of 3mm；
2) regenerative agent is prepared, in the regenerative agent, is calculated in mass percent, includes 5% KOH, 2% FeSO4, 3%
Mg (NO3)2And the water of remaining weight, by KOH, FeSO4、Mg(NO3)2It is uniformly mixed with water.
3) regenerative agent is uniformly sprayed on waste active carbon, the fountain height of regenerative agent is 80kg/t.
4) waste active carbon that processing is completed, which is placed in high temperature furnace, activates, and control high temperature furnace divides three phases to heat up.First temperature
Degree section is drying stage, and at 180 DEG C, time 30min, second temperature section is catabolic phase for temperature control, and temperature is controlled 450
DEG C, time 30min, third temperature section is activation stage, and temperature control is at 750 DEG C, time 60min.It is opened from catabolic phase
Begin, is purged and activated to for desulphurization denitration waste active carbon using vapor, be passed through vapor and give up with for desulphurization denitration
The mass ratio of active carbon sieve is 3:1.
5) charcoal non activated after the completion of activating is cooled to room temperature, and is washed with water and is dried, weighs the regeneration yield of active carbon
It is 94.7%, carries out absorption property test later.
Embodiment 2
The present embodiment is used for the regeneration method of desulphurization denitration waste active carbon, the steps include:
1) by certain steel plant's flue gas desulfurization and denitrification treated waste active carbon, waste active carbon screening removes powdered and grain
Degree is less than the waste active carbon of 3mm；
2) regenerative agent is prepared, in the regenerative agent, is calculated in mass percent, includes 5% KOH, 3% NaOH, 2%
FeSO4, 1% CuSO4, 2% Mg (NO3)2And the water of remaining weight, by KOH, NaOH, FeSO4、CuSO4、Mg(NO3)2
It is uniformly mixed with water.
3) regenerative agent is uniformly sprayed on waste active carbon, the fountain height of regenerative agent is 65kg/t.
4) waste active carbon that processing is completed, which is placed in high temperature furnace, activates, and control high temperature furnace divides three phases to heat up.First temperature
Degree section is drying stage, and at 200 DEG C, time 25min, second temperature section is catabolic phase for temperature control, and temperature is controlled 480
DEG C, time 25min, third temperature section is activation stage, and temperature control is at 780 DEG C, time 50min.It is opened from catabolic phase
Begin, is purged and activated to for desulphurization denitration waste active carbon using vapor, be passed through vapor and give up with for desulphurization denitration
The mass ratio of active carbon sieve is 2:1.
5) charcoal non activated after the completion of activating is cooled to room temperature, and is washed with water and is dried, weighs the regeneration yield of active carbon
It is 95.3%, carries out absorption property test later.
Embodiment 3
The present embodiment is used for the regeneration method of desulphurization denitration waste active carbon, the steps include:
1) by certain steel plant's flue gas desulfurization and denitrification treated waste active carbon, waste active carbon screening removes powdered and grain
Degree is less than the waste active carbon of 3mm；
2) regenerative agent is prepared, in the regenerative agent, is calculated in mass percent, includes 6% KOH, 4% Na2CO3, 2%
FeSO4, 2% CuSO4, 1% Mg (NO3)2, 2% Ba (NO3)2And the water of remaining weight, by KOH, Na2CO3、
FeSO4、CuSO4、Mg(NO3)2、Ba(NO3)2It is uniformly mixed with water.
3) regenerative agent is uniformly sprayed on waste active carbon, the fountain height of regenerative agent is 70kg/t.
4) waste active carbon that processing is completed, which is placed in high temperature furnace, activates, and control high temperature furnace divides three phases to heat up.First temperature
Degree section is drying stage, and at 230 DEG C, time 25min, second temperature section is catabolic phase for temperature control, and temperature is controlled 500
DEG C, time 30min, third temperature section is activation stage, and temperature control is at 800 DEG C, time 40min.It is opened from catabolic phase
Begin, is purged and activated to for desulphurization denitration waste active carbon using vapor, be passed through vapor and give up with for desulphurization denitration
The mass ratio of active carbon sieve is 2:1.
5) charcoal non activated after the completion of activating is cooled to room temperature, and is washed with water and is dried, weighs the regeneration yield of active carbon
It is 95.7%, carries out absorption property test later.
Embodiment 4
The present embodiment is used for the regeneration method of desulphurization denitration waste active carbon, the steps include:
1) by certain steel plant's flue gas desulfurization and denitrification treated waste active carbon, waste active carbon screening removes powdered and grain
Degree is less than the waste active carbon of 3mm；
2) regenerative agent is prepared, in the regenerative agent, is calculated in mass percent, includes 4% KOH, 3% NaOH, 3%
Na2CO3, 2% FeSO4, 2% CuSO4, 3% Ba (NO3)2And the water of remaining weight, by KOH, NaOH, Na2CO3、
FeSO4、CuSO4、Ba(NO3)2It is uniformly mixed with water.
3) regenerative agent is uniformly sprayed on waste active carbon, the fountain height of regenerative agent is 75kg/t.
4) waste active carbon that processing is completed, which is placed in high temperature furnace, activates, and control high temperature furnace divides three phases to heat up.First temperature
Degree section is drying stage, and at 250 DEG C, time 15min, second temperature section is catabolic phase for temperature control, and temperature is controlled 530
DEG C, time 30min, third temperature section is activation stage, and temperature control is at 800 DEG C, time 40min.It is opened from catabolic phase
Begin, is purged and activated to for desulphurization denitration waste active carbon using vapor, be passed through vapor and give up with for desulphurization denitration
The mass ratio of active carbon sieve is 4:1.
5) charcoal non activated after the completion of activating is cooled to room temperature, and is washed with water and is dried, weighs the regeneration yield of active carbon
It is 95.8%, carries out absorption property test later.
Embodiment 5
The present embodiment is used for the regeneration method of desulphurization denitration waste active carbon, the steps include:
1) by certain steel plant's flue gas desulfurization and denitrification treated waste active carbon, waste active carbon screening removes powdered and grain
Degree is less than the waste active carbon of 3mm；
2) regenerative agent is prepared, in the regenerative agent, is calculated in mass percent, includes 7% NaOH, 2% Na2CO3, 2%
CuSO4, 1% Mg (NO3)2, 3% Ba (NO3)2And the water of remaining weight, by NaOH, Na2CO3、FeSO4、CuSO4、
Mg(NO3)2、Ba(NO3)2It is uniformly mixed with water.
3) regenerative agent is uniformly sprayed on waste active carbon, the fountain height of regenerative agent is 65kg/t.
4) waste active carbon that processing is completed, which is placed in high temperature furnace, activates, and control high temperature furnace divides three phases to heat up.First temperature
Degree section is drying stage, and at 235 DEG C, time 20min, second temperature section is catabolic phase for temperature control, and temperature is controlled 550
DEG C, time 20min, third temperature section is activation stage, and temperature control is at 780 DEG C, time 50min.It is opened from catabolic phase
Begin, is purged and activated to for desulphurization denitration waste active carbon using vapor, be passed through vapor and give up with for desulphurization denitration
The mass ratio of active carbon sieve is 3:1.
5) charcoal non activated after the completion of activating is cooled to room temperature, and is washed with water and is dried, weighs the regeneration yield of active carbon
It is 96.9%, carries out absorption property test later.
Control group 1
Original new active carbon is subjected to absorption property test under the same conditions.
Control group 2
Waste active carbon is placed directly in high temperature furnace without spray process, and is controlled and is passed through vapor and is taken off for desulfurization
The mass ratio of nitre waste active carbon sieve is 3:1, is warming up to 800 DEG C and keeps the temperature 4 hours, weighs regenerating for active carbon after taking out cooling
Rate is 89.3%, carries out absorption property test later.
Adsorption capacity test, measuring method are carried out to activated carbon obtained by above-described embodiment and control group are as follows: methylene blue is inhaled
Assignments are measured according to GB/T12496.10-1999；Iodine sorption value is measured according to GB/T12496.8-1999；Four chlorinations
Carbon adsorption value is measured according to GB/T 12496.5-1999.Test result is as shown in table 1.
| Project | Methylene blue adsorption value (mg/g) | Iodine sorption value (mg/g) | Penetrating curve (wt.%) | It regenerates yield (%) |
| Embodiment 1 | 181 | 1335.8±9.86 | 70 | 94.7% |
| Embodiment 2 | 184 | 1346.2±10.73 | 71 | 95.3% |
| Embodiment 3 | 186 | 1357.2±5.89 | 72 | 95.7% |
| Embodiment 4 | 189 | 1362.9±8.52 | 74 | 95.8% |
| Embodiment 5 | 188 | 1381.7±6.64 | 73 | 96.9% |
| Control group 1 | 187 | 1363.5±6.77 | 74 | — |
| Control group 2 | 162 | 1173.7±7.76 | 66 | 89.3% |
As can be seen from the above table, using a kind of regeneration method for desulphurization denitration waste active carbon of the invention, Ke Yiyou
The waste active carbon of regenerative adsorption saturation is imitated, or even further increases the absorption property of active carbon.
The present invention on existing active carbon hot recycling Process ba- sis supplement spray phase, regenerative agent by activator,
Activator promotor, stabilizer and water are made.Activator component is NaOH, KOH and K2CO3One or more mixtures, in high temperature
During activation, sylvite, sodium salt are reduced and are converted into potassium, the metallic vapour of sodium is walked between the synusia of crystallite, strut virtue
Fragrant synusia brings it about distortion or deformation, creates new hole；Stabilizer is Mg (NO3)2With Ba (NO3)2It is one or two kinds of
Mixture can further aoxidize established charcoal and play further oxidation, corrode charcoal body and pore-creating, it is flourishing to form micropore
Microstructure；Activator promotor ingredient is FeSO4With CuSO4One or two kinds of mixtures, the anti-of carbon water reaction can be reduced
Activation energy is answered, the progress of reaction is promoted.In addition, the regenerative process high temperature furnace in waste active carbon divides the three phases temperature rise period.
First temperature section is drying stage, for removing the moisture in waste active carbon；Second temperature section is catabolic phase, useless for decomposing
The organic matter of activated carbon adsorption and the inorganic salts being blocked in hole；Third temperature section is activation stage, for restoring useless activity
The porous structure and adsorption capacity of charcoal.Match obtained regenerative agent Direct Uniform and is sprayed onto waste active carbon surface, it is easy to operate, it is not required to
It is reconfigured dedicated activation equipment.Regeneration method of the present invention for desulphurization denitration waste active carbon, when not only active
Between it is short, to make regenerated carbon that there is preferable mechanical strength, and the absorption property phase of regenerated carbon and new active carbon
When even slightly enhancing.Therefore, method of the invention not only preferably obtain regenerated carbon, but also practical operability compared with
By force, there is good economic and social benefit.
Claims (10)
1. a kind of regenerative agent for desulphurization denitration waste active carbon, which is characterized in that be calculated in mass percent, comprising: 5%~
10% activator, 2%~4% activator promotor, the stabilizer of 1%-3%, remaining is water.
2. a kind of regenerative agent for desulphurization denitration waste active carbon according to claim 1, which is characterized in that activator is
NaOH, KOH and K2CO3One or more of mixtures.
3. a kind of regenerative agent for desulphurization denitration waste active carbon according to claim 1, which is characterized in that activator promotor
For FeSO4With CuSO4One or two kinds of mixtures.
4. a kind of regenerative agent for desulphurization denitration waste active carbon according to claim 1, which is characterized in that stabilizer is
Mg(NO3)2With Ba (NO3)2One or two kinds of mixtures.
5. a kind of regeneration method for desulphurization denitration waste active carbon, which is characterized in that comprise the following processes:
Regenerative agent is uniformly sprayed on and is used for desulphurization denitration waste active carbon, is then activated, is activated to use and divide
Duan Shengwen, temperature-gradient method is divided into drying, decomposition and activation three phases, since catabolic phase, using vapor to for taking off
Sulphur denitration waste active carbon is purged and is activated, and realizes the regeneration for being used for desulphurization denitration waste active carbon；
The regenerative agent is using the regenerative agent for being used for desulphurization denitration waste active carbon described in claim 1-4 any one.
6. a kind of regeneration method for desulphurization denitration waste active carbon according to claim 5, which is characterized in that for taking off
The fountain height of the regenerative agent of sulphur denitration waste active carbon are as follows:
It is per ton that the regenerative agent that desulphurization denitration waste active carbon is used for described in 50~80kg is sprayed for desulphurization denitration waste active carbon.
7. a kind of regeneration method for desulphurization denitration waste active carbon according to claim 5, which is characterized in that drying
When, temperature control is at 180 DEG C~250 DEG C, time 15-30min.
8. a kind of regeneration method for desulphurization denitration waste active carbon according to claim 5, which is characterized in that decompose
When, temperature control is at 450 DEG C~550 DEG C, time 20-30min.
9. a kind of regeneration method for desulphurization denitration waste active carbon according to claim 5, which is characterized in that activation
When, temperature control is at 750 DEG C~800 DEG C, time 40-60min.
10. a kind of regeneration method for desulphurization denitration waste active carbon according to claim 5, which is characterized in that water steams
Gas is (2:1)~(4:1) with the mass ratio for desulphurization denitration waste active carbon.
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| CN110935428A (en) * | 2019-12-16 | 2020-03-31 | 中国科学院过程工程研究所 | Regenerated activated carbon combined by oxidant and pore-forming agent, and preparation method and application thereof |
| CN115624952A (en) * | 2022-09-15 | 2023-01-20 | 城康材料技术有限公司 | Novel carbon material and preparation method and application thereof |
| CN115676827A (en) * | 2022-12-05 | 2023-02-03 | 江苏联兴成套设备制造有限公司 | Method for treating waste activated carbon through calcium-based regulation |
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