CN108855247A - A kind of regeneration method and device of the carbon base catalyst suitable for flue gas purification system - Google Patents
A kind of regeneration method and device of the carbon base catalyst suitable for flue gas purification system Download PDFInfo
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- CN108855247A CN108855247A CN201810903907.7A CN201810903907A CN108855247A CN 108855247 A CN108855247 A CN 108855247A CN 201810903907 A CN201810903907 A CN 201810903907A CN 108855247 A CN108855247 A CN 108855247A
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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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
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/20—Regeneration or reactivation
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/08—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using ammonia or derivatives thereof
-
- 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
Abstract
The regeneration method of the invention discloses a kind of suitable for flue gas purification system carbon base catalyst, wherein, carbon base catalyst is regenerated by regenerator, enter from the top of regenerator, after heated heating, into changeover portion, after the pollutant adsorbed thereon is heated parsing, after cooling section cooling, from regeneration tower bottom discharge；Using inert gas as protection gas in regenerative process；Regeneration method of the present invention injects ammonia before the carbon base catalyst heat temperature raising, participates in the regenerative response of carbon base catalyst.The regeneration that the present invention carries out carbon base catalyst by being passed through ammonia simultaneously in regenerator, the regeneration of absorption sulfuric acid can be participated in using ammonia, it can be effectively reduced the carbon consumption in carbon base catalyst regenerative process, carbon base catalyst after capable of making regeneration simultaneously generates more active groups, to further be activated to carbon base catalyst, its removing ability to pollutant is improved.
Description
Technical field
The present invention is in field of environment engineering, and in particular to urges in flue gas desulfurization and denitrification processing system the charcoal base of adsorption saturation
The regeneration of agent fills method and device.
Background technique
Carbon base catalyst flue gas desulfurization and denitrification technical principle is：Flue gas under the absorption and catalytic action of carbon base catalyst,
SO in flue gas2Carbon base catalyst surface is adsorbed in the form of physical absorption and chemisorption respectively；It is urged simultaneously using charcoal base
The catalytic performance of agent, NO in flue gasxIt has catalytic reduction reaction with ammonia gas and generates N2, realize the desulphurization denitration of flue gas.Desulfurization
Carbon base catalyst after denitration is adsorbed with a large amount of SO2, sulfuric acid and in denitrification process because be passed through ammonia generation ammonium salt, this
A little substances reduce the activity of catalyst, it is therefore necessary to regenerate to active char catalyst is reduced, make desulphurization denitration mistake
The substance parsing adsorbed in journey, to improve the performance of catalyst.Catalyst after regeneration is through the conveying equipments weight such as conveyer
It is new to return in adsorbent equipment, realize recycling for carbon base catalyst.The gas that catalyst regeneration parses can be de- with desulfurization
The form of nitre by-product carries out economic utilization.
According to carbon base catalyst sweetening process common reactant：
It is adsorbed after generating sulfuric acid：SO2+1/2O2+H2O→H2SO4*
SO3+H2O→H2SO4*
It is adsorbed after generating ammonium sulfate： H2SO4*+NH3→NH4HSO4*
NH4HSO4*+NH3→(NH4)2SO4*
Wherein * is indicated：It is adsorbed by carbon base catalyst
Carbon base catalyst regenerative response after adsorbing sulphur：
H2SO4*+1/2C→SO2+1/2CO2+H2O
NH4HSO4*→SO2+1/3N2 +1/3NH3+2 H2During the regeneration of the catalyst, the carbon in carbon base catalyst takes part in O
SO2Resolving reaction, from reaction process as can be seen that catalyst is constantly consumed in the form of chemical wear, because without
Loss of the catalyst in smoke processing system operational process is increased avoidablely.
Meanwhile carbon base catalyst in denitrification process other than as catalyst, also participate in following reaction：
NO+NHxO-AC→N2+H2O+OH-AC
As can be seen that oxygen nitrogen functional group is also the important catalytic activity point of denitration reaction, denitration reaction reduces carbon base catalyst
Active group, the active group after reaction can not be if effective regeneration, and carbon base catalyst activity will gradually reduce.Separately
Outside, during combined desulfurization and denitration, due to SO2Presence, the denitration performance of carbon base catalyst is substantially reduced, therefore, effectively
The performance of regenerated catalyst is improved with regard to particularly important.
Existing regenerator technical solution (such as Chinese patent:107,510,218 107537591 A of A, CN of CN) in, mainly
Catalyst is regenerated by heating method, inert gas such as N is used in regenerative process2Gas will be solved as protection gas
Gassing body carrying device.Such design is disadvantageous in that：1）Although can be realized the parsing of Catalyst Adsorption substance and divide
From, but since the carbon in carbon base catalyst takes part in SO2Resolving reaction, result in the increase of catalyst consumption；2）Due to
The active group of catalyst gradually decreases in denitrification process, might not be only able to achieve in catalyst by heating method living
The effective regeneration of property group.
Summary of the invention
The purpose of the present invention is to solve defect existing in the prior art, it one kind is provided can effectively improve charcoal base and urge
The method of agent regenerability.
In order to achieve the above object, the regeneration of the present invention provides a kind of suitable for flue gas purification system carbon base catalyst
Method, wherein carbon base catalyst is regenerated by regenerator, is entered from the top of regenerator, after heated heating, was entered
Section is crossed, after the pollutant adsorbed thereon is heated parsing, after cooling section cooling, from regeneration tower bottom discharge；It regenerated
Using inert gas as protection gas in journey；Regeneration method of the present invention injects ammonia before the carbon base catalyst heat temperature raising,
Participate in the regenerative response of carbon base catalyst.
Further, the injection rate of ammonia is advisable with adapting to denitrating flue gas efficiency requirements, but the NO in injection rate and flue gasx
Content molar ratio is no more than 1；Passed through at the top and bottom of regenerator using inert gas as protection gas in the regenerative process
Inert gas is realized simultaneously；The injection rate of inert gas need to meet the requirement for preventing regenerating unit overtemperature at the top of the regenerator,
And it can make to parse the SO in gas2Concentration is 15% or so, it is contemplated that the mixed effect of ammonia, preferentially take under equal conditions compared with
The injection rate of big flow, bottom inert gas is identical with top inert gas injection rate.
Further, the regeneration temperature of carbon base catalyst is controlled at 400-450 DEG C.
The regenerating unit of the present invention also provides a kind of suitable for flue gas purification system carbon base catalyst, the regenerating unit
Using regenerator, the regenerator is divided into bringing-up section, changeover portion and cooling section；The tube side part of regenerator, top are equipped with charcoal base
Catalyst inlet, bottom are exported equipped with carbon base catalyst, and changeover portion, which is equipped with, parses gas vent, above bringing-up section and under cooling section
Side, is respectively equipped with inert gas first entrance and inert gas second entrance；The shell side part of regenerator, heating pars infrasegmentalis are equipped with
Heating gas inlet, top are exported equipped with heat gas, and cooling pars infrasegmentalis is equipped with cooling gas inlet, and top is equipped with cooling gas
Outlet；It is additionally provided with ammonia inlet on regenerator of the present invention, is connected with the inside of the regenerator；Ammonia inlet position
Above the bringing-up section of regenerator or the ammonia inlet is the inert gas first entrance；The regenerating unit is also
Including ammonia injection pipe, the first inert gas injection pipe and the second inert gas injection pipe；Ammonia injection pipe both ends difference
Connect the ammonia inlet and ammonia source；The ammonia injection pipe is equipped with valve and flow control meter；First inertia
Gas injection tube and the second inert gas injection pipe are connected with inert gas first entrance and inert gas second entrance respectively,
On be equipped with valve and flow control meter.
Further, preheating section is additionally provided with above the bringing-up section of regenerator；The ammonia inlet is located at the preheating section
Between bringing-up section or the ammonia inlet is the inert gas first entrance and is located above the preheating section.
Further, regenerating unit further includes ammonia even distribution device；The ammonia even distribution device is injected set on the ammonia
At mouthful.
Further, the carbon base catalyst entrance of regenerator and carbon base catalyst exit are respectively equipped with duplex blocking valve.
Further, ammonia even distribution device includes connecting flange, Guan Zhen, gas pipeline, device housing and tube sheet；Tube sheet is solid
Surely it is set in device housing；Guan Zhen is using in staggered manner arrangement tube sheet；Gas pipeline be it is multiple, be arranged in parallel in device housing
On, one end is connected with corresponding connecting flange, and one end is connected with the Guan Zhen on tube sheet；Ammonia even distribution device passes through connecting flange
It is fixed on regenerator.Gas pipeline spacing takes 500mm, and bore takes 15 ~ 25mm.Tube plate thickness is about gas pipeline spacing
0.25 ~ 3 times, preferably 1 times.Ammonia is entered in ammonia even distribution device by gas pipeline.Formed Guan Zhen bore be not less than
70mm, preferably 75 ~ 90mm, tube center distance are about 1.5 times of calibers.
The present invention has the following advantages that compared with prior art：
The regeneration that the present invention carries out carbon base catalyst by being passed through ammonia simultaneously in regenerator, can participate in absorption sulphur using ammonia
The regeneration of acid, can be effectively reduced the carbon consumption in carbon base catalyst regenerative process, while can make the carbon base catalyst after regeneration
More active groups are generated, to further be activated to carbon base catalyst, improve its removing ability to pollutant.Together
Shi Liyong flow control meter controls the ammonia and nitrogen flow of injection, realizes the economy of flue gas desulfurization and denitrification processing system
Efficient operation.
Detailed description of the invention
Fig. 1 is a kind of knot of the regenerating unit of the carbon base catalyst suitable for flue gas purification system in the embodiment of the present invention 1
Structure schematic diagram；
Fig. 2 is another structural schematic diagram of regenerating unit in the embodiment of the present invention 2；
Fig. 3 is the structural schematic diagram of ammonia even distribution device in Fig. 1；
Fig. 4 is the pipe battle array distribution schematic diagram of ammonia even distribution device in Fig. 3.
In figure, 1- preheating section, 2- bringing-up section, 3- changeover portion, 4- cooling section, 5- duplex blocking valve, 6- ammonia even distribution device,
7- connecting flange, 8- pipe battle array, 9- device housing, 10- tube sheet, 11- gas pipeline.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawing.
Embodiment 1
As shown in Figure 1, the regenerating unit of present invention carbon base catalyst suitable for flue gas purification system uses existing regenerator
It improves.Existing regenerator is divided into preheating section 1, bringing-up section 2, changeover portion 3, cooling section 4 from top to bottom.The charcoal of adsorption saturation
Base catalyst passes through the duplex blocking valve 5 on top（Prevent the gas exchanges inside and outside device）Into in regenerator, preheated section 1 real
It now preheats, wherein preheating section 1 is pipe shell type heat exchange structure, and wherein carbon base catalyst walks tube side, and preheating gas walks shell side, pre- hot gas
The exit gas of cooling section 4 can be used in body.Carbon base catalyst is realized for heated section 2 again is warming up to regeneration temperature, usually takes 400-
450 DEG C, bringing-up section uses pipe shell type heat exchange structure, and wherein carbon base catalyst walks tube side, and heat gas walks shell side, and heat gas can
Using the high-temperature flue gas of hot-air or hot-blast stove generation after electric heating.Carbon base catalyst after regeneration is through changeover portion 3（Constant temperature
Area）, the parsing gas that generates in regenerative process（SRG）It is discharged from the SRG gas vent of changeover portion 3.Carbon base catalyst enters back into
Cooling section 4 is cooling after being regenerated, and cooling section 4 also uses pipe shell type heat exchange structure, and carbon base catalyst walks tube side, and cooling gas is walked
Shell side, cooling gas use air.Carbon base catalyst after cooling is discharged through duplex blocking valve 5 from regeneration tower bottom.Simultaneously again
Inert gas is respectively set in the inlet and exit of raw tower（Generally use nitrogen）Inlet, the inert gas of injection is as guarantor
Gas is protected, carbon base catalyst is can protect and reduces scaling loss in heating regenerative process and prevent from catching fire, and will again as delivery gas
The parsing gas discharge discharged during raw.
Ammonia even distribution device 6, ammonia is arranged in regenerating unit of the present invention before the lower part of the preheating section 1 of regenerator, the entrance of bringing-up section 2
After gas is injected by ammonia even distribution device, walks in tube side injection regenerator, bringing-up section 2 is entered after sufficiently spreading, is urged with charcoal base
Agent flows downward jointly, participates in the regenerative process of carbon base catalyst.
According to one of the regenerative response of sulfuric acid：
H2SO4*+NH3→NH4HSO4*
NH4HSO4*→SO2+1/3N2 +1/3NH3+2 H2O
The sulfuric acid of absorption is reacted with the ammonia of injection generates NH4HSO4, NH4HSO4It can directly be regenerated, without consuming carbon, be dropped
Carbon consumption in low carbon base catalyst regenerative process, to reduce the consumption of carbon base catalyst.
In addition, the carbon base catalyst regenerative response in regenerator further includes：
SO3+C※→2SO2+O-C※
NH3+O-C※→N2+OH-C
NH3+O-C※→H2O+N-O-C※
Wherein, ※ indicates the carbon in carbon base catalyst.
As can be seen that the ammonia of injection can effectively facilitate nitrogen in carbon base catalyst after entering regenerating unit bringing-up section
The generation of oxygen functional group, the carbon base catalyst after making regeneration have more denitration catalyst active sites, urge to realize charcoal base
The progress of agent further activates, and improves it to NOxRemoving ability.
As shown in figure 3, ammonia even distribution device 6 includes connecting flange 7, pipe battle array 8, gas pipeline 11, device housing 9 and tube sheet
10.Gas pipeline more than 8, in device housing 9, one end is connected parallel arrangement with corresponding connecting flange 7, one end and tube sheet 10
On Guan Zhen be connected.Ammonia even distribution device 6 is fixed on regenerator by connecting flange 7.8 spacing of gas pipeline takes 500mm,
Bore takes 15 ~ 25mm.10 thickness of tube sheet is about 0.25 ~ 3 times of 8 spacing of gas pipeline, preferably 1 times.Ammonia passes through flue
Road 11 enters in ammonia even distribution device 6.Tube sheet 10 is fixed in device housing.Guan Zhen arranges tube sheet 10 using staggered manner
In, the bore for forming Guan Zhen is not less than 70mm, preferably 75 ~ 90mm, and tube center distance is about 1.5 times of calibers.
In order to which preferably the injection rate of nitrogen is adjusted, the present invention passes through ammonia injection pipe（It is not drawn into）It is equal with ammonia
Cloth apparatus 6 is connected, and valve and flow control meter are equipped on ammonia injection pipe, and the on-off and flow for carrying out ammonia injection are adjusted.
The inlet and exit for injecting inert gas into regenerator by inert gas injection pipe respectively simultaneously, in inlet and outlet
It is respectively provided with valve and flow control meter on the inert gas injection pipe at place, carries out the on-off of injection nitrogen and flow up and down and adjusts.
Embodiment 2
As shown in Fig. 2, with embodiment 1, difference is the structure of regenerating unit in the present embodiment, ammonia even distribution device 6 is set to
At the inert gas inlet of regenerator inlet, ammonia reinjects in regenerating unit after mixing with nitrogen.Ammonia and nitrogen point
It is not connected to after being mixed in filling main to be injected by ammonia even distribution device 6 by ammonia injection pipe and nitrogen injection pipe and regenerate
In tower.The gas being passed through by the valve and flow control meter that are arranged on respective injection pipe, carry out injection gas on-off and
Flow is adjusted.
Regenerating unit of the present invention can also be not provided with preheating section 1, and the ammonia injected at this time is directly entered bringing-up section 2 and participates in charcoal base
The regenerative response of catalyst.
Claims (8)
1. a kind of regeneration method of the carbon base catalyst suitable for flue gas purification system, the carbon base catalyst by regenerator into
Row regeneration, enters, after heated heating, into changeover portion, the pollutant adsorbed thereon is heated parsing from the top of regenerator
Afterwards, after using cooling section cooling, from regeneration tower bottom discharge；Using inert gas as protection gas in regenerative process；It is special
Sign is：The regeneration method injects ammonia before the carbon base catalyst heat temperature raising, and the regeneration for participating in carbon base catalyst is anti-
It answers.
2. regeneration method according to claim 1, it is characterised in that：The controlling of injecting quantity of the ammonia exists：The ammonia
With NO in flue gas to be cleanxThe molar ratio of content is no more than 1；Passed through using inert gas as protection gas in the regenerative process
Inert gas is realized simultaneously at the top and bottom of regenerator；The injection rate phase phase of inert gas at the top and bottom of the regenerator
Together, and to parse the SO in gas2Concentration is controlled in 12-17%.
3. regeneration method according to claim 2, it is characterised in that：The regeneration temperature control of the carbon base catalyst exists
400-450℃。
4. a kind of regenerating unit of the carbon base catalyst suitable for flue gas purification system, the regenerating unit uses regenerator, institute
It states regenerator and is divided into bringing-up section, changeover portion and cooling section；The tube side part of regenerator, top are equipped with carbon base catalyst entrance, bottom
Portion is exported equipped with carbon base catalyst, and changeover portion is equipped with parsing gas vent, and bringing-up section top is respectively equipped with lazy with below cooling section
Property gas first entrance and inert gas second entrance；The shell side part of regenerator, heating pars infrasegmentalis are equipped with heating gas inlet,
Top is exported equipped with heat gas, and cooling pars infrasegmentalis is equipped with cooling gas inlet, and top is exported equipped with cooling gas；Its feature exists
In：It is additionally provided with ammonia inlet on the regenerator, is connected with the inside of the regenerator；The ammonia inlet is located at again
Above the bringing-up section of raw tower or the ammonia inlet is the inert gas first entrance；The regenerating unit further includes
Ammonia injection pipe, the first inert gas injection pipe and the second inert gas injection pipe；Ammonia injection pipe both ends are separately connected
The ammonia inlet and ammonia source；The ammonia injection pipe is equipped with valve and flow control meter；First inert gas
Injection pipe and the second inert gas injection pipe are connected with inert gas first entrance and inert gas second entrance respectively, thereon
Equipped with valve and flow control meter.
5. regenerating unit according to claim 4, it is characterised in that：Preheating is additionally provided with above the bringing-up section of the regenerator
Section；The ammonia inlet is between the preheating section and bringing-up section or the ammonia inlet is the inert gas
First entrance and it is located above the preheating section.
6. regenerating unit according to claim 5, it is characterised in that：The regenerating unit further includes ammonia even distribution device；
The ammonia even distribution device is set at the ammonia inlet.
7. regenerating unit according to claim 6, it is characterised in that：The carbon base catalyst entrance and charcoal base of the regenerator
Duplex blocking valve is respectively equipped at catalyst outlet.
8. regenerating unit according to claim 7, it is characterised in that：The ammonia even distribution device includes connecting flange, pipe
Battle array, gas pipeline, device housing and tube sheet；Tube sheet is fixed in device housing；Guan Zhen is using in staggered manner arrangement tube sheet；
Gas pipeline be it is multiple, in device housing, one end is connected parallel arrangement with corresponding connecting flange, the pipe on one end and tube sheet
Battle array is connected；Ammonia even distribution device is fixed on regenerator by connecting flange.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810903907.7A CN108855247A (en) | 2018-08-09 | 2018-08-09 | A kind of regeneration method and device of the carbon base catalyst suitable for flue gas purification system |
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| CN201810903907.7A CN108855247A (en) | 2018-08-09 | 2018-08-09 | A kind of regeneration method and device of the carbon base catalyst suitable for flue gas purification system |
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| CN109260949A (en) * | 2018-11-29 | 2019-01-25 | 国电环境保护研究院有限公司 | A kind of fire retardant anticorrosion erosion regenerator |
| CN109908757A (en) * | 2019-04-18 | 2019-06-21 | 国电环境保护研究院有限公司 | A kind of carbon base catalyst regenerating unit and regeneration method |
| CN110038646A (en) * | 2019-05-30 | 2019-07-23 | 国电环境保护研究院有限公司 | A kind of carbon base catalyst regenerating unit and technique |
| CN114797998A (en) * | 2022-04-13 | 2022-07-29 | 成都达奇环境科技有限公司 | Catalyst washing and regenerating method for catalytic flue gas desulfurization device |
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