CN105435599A - Pollution gas treatment system and treatment method - Google Patents
Pollution gas treatment system and treatment method Download PDFInfo
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- CN105435599A CN105435599A CN201510943820.9A CN201510943820A CN105435599A CN 105435599 A CN105435599 A CN 105435599A CN 201510943820 A CN201510943820 A CN 201510943820A CN 105435599 A CN105435599 A CN 105435599A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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Abstract
The invention relates to a pollution gas treatment system and treatment method based on a chemical looping combustion principle; the pollution gas treatment system includes a first chemical looping combustion reactor, a second chemical looping combustion reactor, gas pipelines and three-way valves; the chemical looping combustion reactors are filled with oxygen carriers; the gas pipelines include a pollution gas pipeline, an air pipeline, a reduction reaction product gas pipeline and an oxidation reaction product gas pipeline; pollution gas contains hydrogen sulfide and other sulfur compounds or ammonia, trimethylamine and other amines. The treatment method includes the following steps: the pollution gas and the oxidation-state oxygen carrier undergo a reduction reaction, oxygen and the reduction-state oxygen carrier or metal sulfides undergo an oxidizing regeneration reaction, when the gas concentration in the two chemical looping combustion reactors reaches a set value, the three-way valves are switched, and treatment goes into a next cycle. The oxygen carriers with suitable oxidation ability are selected, in the process of pollution gas treatment, NOx is not generated, SO2 can be captured, the treatment conditions are easy to control, and the device and the method are more suitable for practical application.
Description
Technical field
The present invention relates to a kind of gas handling system, particularly relate to a kind for the treatment of system and processing method of the dusty gas based on burning chemistry chains principle.
Background technology
In the daily production of people and life, can produce a lot of dusty gas, the foul smell etc. that the waste gas that the waste gas that such as industrial production produces, painting workshop produce, garbage loading embeading produce, the harmful components kind in these waste gas is a lot, mainly comprises H
2the sulphur compound such as S, methyl mercaptan, NH
3and the amine such as trimethylamine, butanediamine, the various volatile organic matter such as " triphen ", formaldehyde (VOCs) gas etc.These contamination gases know from experience the life of resident near puzzlement, also cause the adverse effects such as photochemical fog, acid rain, greenhouse effects to environment, and therefore the research and development of dusty gas treatment system are efficiently the focuses of research always.
At present, for H
2s, NH
3absorption method, Production by Catalytic Combustion Process and burning method etc. are mainly contained with the treatment technology of the dusty gas such as VOCs.Absorption method is suitable for purifying the large but dusty gas that harmful substance contents is low of quantity, but the adsorbent of the method saturated after need to carry out desorption and regeneration, the H parsed
2s, NH
3harmless treatment is needed Deng still; Production by Catalytic Combustion Process contains H in process
2during the dusty gas of the sulphur compounds such as S, H
2the SO that the oxidation such as S generates
2by the N in combustion air
2and other reaction product gas diluted, concentration does not rise counter falling, thus adds cost and the energy consumption of follow-up sulfur removal technology, in addition, and H
2s etc. also easily make catalyst poisoning and cause catalytic activity to reduce.At process NH
3time, if adopt selective catalytic oxidation method (SCO) to carry out denitrogenation (by NH
3be converted into N
2), due to its reaction temperature width, so need strict Controlling Technology condition, otherwise easily produce NO
x, cause the selective decline of denitrogenation.In addition, when harmful components fluctuation of concentration is larger in dusty gas, needs adjustment combustion-supporting air quantity in time to guarantee suitable air-fuel ratio, otherwise the resolution ratio of harmful substance can be caused to decline, therefore very high to the requirement of process regulation.Burning method is high due to ignition temperature, often needs to add auxiliary fuel due to the calorific value deficiency of dusty gas, and NH
3or amine can at high temperature be converted into fuel type NO
x.
Comprehensively existing to H
2the sulphur compound such as S, methyl mercaptan, NH
3and the amine such as trimethylamine, butanediamine, there is easy generation catalyst sulfur poisoning, easily generate NO in the processing method of the dusty gas such as the various VOCs gases such as " triphen ", formaldehyde
xthe problems such as high are required with to process regulation.
Summary of the invention
Main purpose of the present invention is, there is provided a kind for the treatment of system and processing method of dusty gas, technical problem to be solved is the process adopting the principle of burning chemistry chains to carry out dusty gas, makes it in processing procedure, there will not be oxygen carrier sulfur poisoning, do not generate NO
x, process conditions are easy to control, thus are more suitable for practicality.
The object of the invention to solve the technical problems realizes by the following technical solutions.
The treatment system of a kind of dusty gas proposed according to the present invention, comprises the 1st burning chemistry chains reactor, the 2nd burning chemistry chains reactor, gas pipeline and triple valve; Oxygen carrier is filled with in the 1st described burning chemistry chains reactor and the 2nd burning chemistry chains reactor; Described gas pipeline comprises dusty gas pipeline, air duct, reduction reaction product gas pipeline and oxidation reaction product gas pipeline; Described dusty gas contains one or more harmful components in the amines such as the sulphur compounds such as hydrogen sulfide, ammonia and trimethylamine.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Preferably, the treatment system of aforesaid dusty gas, wherein said oxygen carrier is the one or more kinds of mixtures in copper base load oxysome, iron-based oxygen carrier and Ni-based oxygen carrier.
Preferably, the treatment system of aforesaid dusty gas, the active material of wherein said copper base load oxysome is CuO, and carrier is Al
2o
3, SiO
2or TiO
2in one or more kinds of mixtures; The active material of iron-based oxygen carrier is Fe
2o
3, carrier is Al
2o
3, SiO
2or TiO
2in one or more kinds of mixtures; The active material of Ni-based oxygen carrier is NiO, and carrier is Al
2o
3, SiO
2or TiO
2in one or more kinds of mixtures.
Preferably, the treatment system of aforesaid dusty gas, wherein said dusty gas is simultaneously also containing one or more in the volatile organic matter such as benzene,toluene,xylene and formaldehyde.
Preferably, the treatment system of aforesaid dusty gas, also comprises sulfur dioxide capturing device, and it is arranged on described oxidation reaction product gas pipeline.
Preferably, the treatment system of aforesaid dusty gas, wherein said sulfur dioxide capturing device is make the dry desulfurization device of desulfurizing agent, the wet desulphurization device making desulfurizing agent with limestone/lime slurries or concentrated sulfuric acid process units with calcium oxide.
The object of the invention to solve the technical problems also adopts following technical scheme to realize.
The treatment system of a kind of dusty gas proposed according to the present invention, comprises
(1) reduction process of oxidation state oxygen carrier, makes described dusty gas enter in the 1st described burning chemistry chains reactor by described dusty gas pipeline, with described oxygen carrier generation reduction reaction;
(2) oxidative regeneration process of reduction-state oxygen carrier or metal sulfide, make air, oxygen enrichment or purity oxygen enter in the 2nd described burning chemistry chains reactor by described air, oxygen enrichment or purity oxygen pipeline, react with reduction-state oxygen carrier or metal sulfide generation oxidation regeneration;
(3) handoff procedure of burning chemistry chains reactor, harmful components concentration in the product of the reduction reaction in the 1st burning chemistry chains reactor reaches setting value, when oxygen concentration in the product of the oxidation reaction in the 2nd burning chemistry chains reactor reaches setting value, switch three-way valve, make described dusty gas enter the 2nd described burning chemistry chains reactor, air, oxygen enrichment or purity oxygen enter the 1st described burning chemistry chains reactor.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Preferably, the treatment system of aforesaid dusty gas, also comprises and being trapped by the described sulfur dioxide capturing device of the sulfur dioxide in the product of described oxidation reaction.
Preferably, the treatment system of aforesaid dusty gas, the temperature of wherein said reduction reaction is 200 DEG C ~ 500 DEG C; The temperature of described oxidation regeneration reaction is 150 DEG C ~ 500 DEG C.
By technique scheme, treatment system and the processing method of dusty gas of the present invention at least have following advantages:
(1) desulfurization trapping and the SO of sulphur compound in dusty gas can be realized
2enrichment.In reduction process, H
2sulphur in the sulphur compounds such as S is captured down with the form of metal sulfide.In oxidative regeneration process then, SO can be realized by passing into oxygen enrichment
2enrichment method, thus cost and the energy consumption of follow-up dry method or wet desulfurizing process can be saved.If pass into purity oxygen, pure SO can be obtained
2, can the concentrated sulfuric acid etc. be translated into, thus realize SO
2effective utilization;
(2) the selective height of ammonia and amine denitrogenation, denitrification effect is remarkable.For the denitrogenation of ammonia and amine, compared with the oxidability that oxygen is excessively strong, the oxidation state of the oxygen carriers such as copper base has strong and weak suitable oxidability, can by NH
3be oxidized to the nitrogen of zeroth order with the nitrogen in amine, and be difficult to be further oxidized to the NO of positive divalence or the NO of positive tetravalence
2;
(3) compared with Production by Catalytic Combustion Process, the present invention can provide a large amount of Lattice Oxygen and control without the need to carrying out air-fuel ratio due to oxygen carrier, thus has the significantly advantage such as stable, easy and simple to handle for the process of oxygen-free gas or the concentration of oxygen and harmful components and the dusty gas of flow fluctuation;
(4) different from Production by Catalytic Combustion Process, can not there is sulfur poisoning in oxygen carrier.The active component metal oxide of oxygen carrier is a large amount of, although in course of reaction meeting and H
2s etc. generate metal sulfide, but again can be converted into metal oxide in oxidation regeneration reaction subsequently, thus there is not the problem of oxygen carrier sulfur poisoning.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technological means of the present invention, and can be implemented according to the content of description, coordinates accompanying drawing to be described in detail as follows below with preferred embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the treatment system of embodiment 1 dusty gas.
Fig. 2 is the schematic diagram of the treatment system of embodiment 2-4 dusty gas.
Fig. 3 is the schematic diagram of the treatment system of embodiment 5-7 dusty gas.
Detailed description of the invention
For further setting forth the present invention for the technological means reaching predetermined goal of the invention and take and effect, below in conjunction with accompanying drawing and preferred embodiment, to treatment system and its detailed description of the invention of processing method, structure, feature and effect thereof of a kind of dusty gas proposed according to the present invention, be described in detail as follows.In the following description, the not necessarily same embodiment that different " embodiment " or " embodiment " refers to.In addition, special characteristic, structure or feature in one or more embodiment can be combined by any suitable form.
Embodiment 1
Please refer to Fig. 1.The treatment system of shown dusty gas comprises: the 1st burning chemistry chains reactor 101 being filled with the oxidation state 107 of copper base load oxysome, the 2nd burning chemistry chains reactor 102 of reduction-state 108 being filled with copper base load oxysome, dusty gas pipeline 109, air blower 111, air duct 112, reduction reaction product gas pipeline 110, oxidation reaction product gas pipeline 113 and electric T-shaped valve group 103 ~ 106.The active material of described copper base load oxysome is CuO, and carrier is SiO
2.Described dusty gas contains NH
3.
The triple valve 103 of dusty gas on dusty gas pipeline 109 enters in the 1st burning chemistry chains reactor 101, with oxidation state oxygen carrier 107, reduction reaction occurs: the NH in dusty gas
3react with oxidation state oxygen carrier 107 and generate nitrogen and steam, simultaneous oxidation state oxygen carrier 107 is converted into reduction-state; The triple valve 104 of reduction reaction product gas on reduction reaction product gas pipeline 110 is discharged.The temperature of described reduction reaction is 200 DEG C.
The triple valve 105 of air on air duct 112 enters in the 2nd burning chemistry chains reactor 102, carries out oxidation regeneration reaction with reduction-state oxygen carrier 108, and reduction-state oxygen carrier 108 generates oxidation state oxygen carrier with the oxygen reaction in air.The triple valve 106 of oxidation reaction product gas on oxidation reaction product gas pipeline 113 is discharged.Described oxidation regeneration reaction temperature is 150 DEG C.
When the whole or major part of the oxidation state oxygen carrier 107 in the 1st burning chemistry chains reactor 101 is converted into reduction-state oxygen carrier, the total concentration of the harmful components namely in reduction reaction product gas reaches setting value 10mg/m
3whole or the major part of the reduction-state oxygen carrier 108 simultaneously in the 2nd burning chemistry chains reactor 102 is converted into oxidation state oxygen carrier, namely when the oxygen concentration in oxidation reaction product gas reaches setting value 2%, carry out the switching of electric T-shaped valve group 103 ~ 106, dusty gas is entered in the 2nd burning chemistry chains reactor 102 through triple valve 103, and air enter in the 1st burning chemistry chains reactor 101 through triple valve 105.By to each pipeline gas flow and the reasonable setting of each valve transfer time, the continuous process of dusty gas can be realized.
The oxidation state of copper base load oxysome and NH
3reduction reaction, and reduction-state and O
2oxidation regeneration reaction reaction equation and reaction temperature under standard free energy change and reaction heat as follows:
3CuO+2NH
3(g)＝3Cu+N
2(g)+3H
2O(g)△G°＝-78.56kcal/mol
△H°＝-40.05kcal/mol
2Cu+O
2(g)＝2CuO△G°＝-55.72kcal/mol
△H°＝-74.16kcal/mol
Embodiment 2
Please refer to Fig. 2.The present embodiment is compared with embodiment 1, and difference is: oxygen carrier is iron-based oxygen carrier, and its active material is Fe
2o
3, carrier is Al
2o
3.The temperature of reduction reaction and oxidation reaction is 300 DEG C.Oxidation reaction product gas pipeline 113 arranges sulfur dioxide capturing device 200, is used for trapping the SO in oxidation reaction product gas
2, described sulfur dioxide capturing device 200 is the wet desulphurization device making desulfurizing agent with the slurries of lime stone or lime.Dusty gas contains trimethylamine and H
2s.
The oxidation state of iron-based oxygen carrier and trimethylamine and H
2the reduction reaction of S, and reduction-state and iron sulfide and O
2oxidation regeneration reaction reaction equation and reaction temperature under standard free energy change and reaction heat as follows:
63Fe
2O
3+2C
3H
9N(g)＝42Fe
3O
4+N
2(g)+9H
2O(g)+6CO
2(g)
Fe
2O
3+3H
2S(g)＝Fe
2S
3+3H
2O(g)△G°＝-29.12kcal/mol
△H°＝-34.20kcal/mol
4Fe
3O
4+O
2(g)＝6Fe
2O
3△G°＝-74.26kcal/mol
△H°＝-111.95kcal/mol
Fe
2S
3+4.5O
2(g)＝Fe
2O
3+3SO
2(g)△G°＝-310.75kcal/mol
△H°＝-337.83kcal/mol
Embodiment 3
Please refer to Fig. 2.The present embodiment is compared with embodiment 2, and difference is: oxygen carrier is Ni-based oxygen carrier, and its active material is NiO, and carrier is TiO
2.The temperature of reduction reaction and oxidation reaction is 350 DEG C, and oxidation reaction product gas pipeline 113 arranges sulfur dioxide capturing device 200, is used for trapping the SO in oxidation reaction product gas
2, described sulfur dioxide capturing device 200 is the dry desulfurization device making desulfurizing agent with calcium oxide.Dusty gas contains methyl mercaptan and toluene.
The reduction reaction of the oxidation state of Ni-based oxygen carrier and methyl mercaptan and toluene, and reduction-state and nickel sulfide and O
2oxidation regeneration reaction reaction equation and reaction temperature under standard free energy change and reaction heat as follows:
4NiO+CH
3SH(g)＝NiS+3Ni+CO
2+2H
2O(g)
△G°＝-43.90kcal/mol
△H°＝2.50kcal/mol
18NiO+C
7H
8(g)＝18Ni+7CO
2(g)+4H
2O(g)
Ni+O
2(g)＝NiO△G°＝-86.90kcal/mol
△H°＝-113.44kcal/mol
NiS+1.5O
2(g)＝NiO+SO
2(g)△G°＝-96.07kcal/mol
△H°＝-107.18kcal/mol
Embodiment 4
Please refer to Fig. 2.The present embodiment is compared with embodiment 2, and difference is: oxygen carrier is the mixture of copper base load oxysome and iron-based oxygen carrier, and carrier is Al
2o
3and SiO
2mixture, dusty gas is ammonia, benzene,toluene,xylene and formaldehyde.The temperature of reduction reaction and oxidation reaction is 400 DEG C.Oxidation reaction product gas pipeline 113 arranges sulfur dioxide capturing device 200, is used for trapping the SO in oxidation reaction product gas
2, described sulfur dioxide capturing device 200 is the dry desulfurization device making desulfurizing agent with calcium oxide.
Embodiment 5
Please refer to Fig. 3.The present embodiment is compared with embodiment 3, and difference is: oxygen carrier is the mixture of copper base load oxysome and Ni-based oxygen carrier, and carrier is SiO
2and TiO
2mixture, dusty gas is hydrogen sulfide, ammonia, benzene,toluene,xylene and formaldehyde.The temperature of reduction reaction and oxidation reaction is 450 DEG C.Air duct 112 is changed to oxygen rich gas pipeline 300, oxidation reaction product gas pipeline 113 arranges sulfur dioxide capturing device 200, be used for trapping the SO in oxidation reaction product gas
2, described sulfur dioxide capturing device 200 is concentrated sulfuric acid process units.
Embodiment 6
Please refer to Fig. 3.The present embodiment is compared with embodiment 3, and difference is: oxygen carrier is the mixture of iron-based oxygen carrier and Ni-based oxygen carrier, and carrier is Al
2o
3and TiO
2mixture, dusty gas is hydrogen sulfide, methyl mercaptan, ammonia, trimethylamine, butanediamine, benzene,toluene,xylene and formaldehyde.The temperature of reduction reaction and oxidation reaction is 500 DEG C.Air duct 112 is changed to pure oxygen gas pipeline 300, oxidation reaction product gas pipeline 113 arranges sulfur dioxide capturing device 200, be used for trapping the SO in oxidation reaction product gas
2, described sulfur dioxide capturing device 200 is concentrated sulfuric acid process units.
Embodiment 7
Please refer to Fig. 3.The present embodiment is compared with embodiment 6, and difference is: oxygen carrier is the mixture of copper base load oxysome, iron-based oxygen carrier and Ni-based oxygen carrier.Carrier is Al
2o
3, SiO
2and TiO
2mixture, dusty gas is hydrogen sulfide, cos, methyl mercaptan, ammonia, trimethylamine, butanediamine, benzene,toluene,xylene and formaldehyde.
The above, it is only preferred embodiment of the present invention, not do any pro forma restriction to the present invention, any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (9)
1. a treatment system for dusty gas, is characterized in that:
Comprise the 1st burning chemistry chains reactor, the 2nd burning chemistry chains reactor, gas pipeline and triple valve; Oxygen carrier is filled with in the 1st described burning chemistry chains reactor and the 2nd burning chemistry chains reactor; Described gas pipeline comprises dusty gas pipeline, air duct, reduction reaction product gas pipeline and oxidation reaction product gas pipeline; Described dusty gas contains one or more harmful components in sulphur compound, ammonia and amine.
2. the treatment system of dusty gas according to claim 1, is characterized in that:
Described oxygen carrier is the one or more kinds of mixtures in copper base load oxysome, iron-based oxygen carrier and Ni-based oxygen carrier.
3. the treatment system of dusty gas according to claim 2, is characterized in that:
The active material of described copper base load oxysome is CuO, and carrier is Al
2o
3, SiO
2or TiO
2in one or more kinds of mixtures;
The active material of described iron-based oxygen carrier is Fe
2o
3, carrier is Al
2o
3, SiO
2or TiO
2in one or more kinds of mixtures;
The active material of described Ni-based oxygen carrier is NiO, and carrier is Al
2o
3, SiO
2or TiO
2in one or more kinds of mixtures.
4. the treatment system of dusty gas according to claim 1, is characterized in that:
Described dusty gas is simultaneously also containing one or more the mixture in volatile organic matter dusty gas.
5. the treatment system of the dusty gas according to any one of claim 1-4, is characterized in that:
Also comprise sulfur dioxide capturing device, it is arranged on described oxidation reaction product gas pipeline.
6. the treatment system of dusty gas according to claim 5, is characterized in that:
Described sulfur dioxide capturing device is make the dry desulfurization device of desulfurizing agent, the wet desulphurization device making desulfurizing agent with limestone/lime slurries or concentrated sulfuric acid process units with calcium oxide.
7. a processing method for dusty gas, adopts the treatment system of the dusty gas described in any one of claim 1-6, it is characterized in that: comprise,
(1) reduction process of oxidation state oxygen carrier, makes described dusty gas enter in the 1st described burning chemistry chains reactor by described dusty gas pipeline, with described oxygen carrier generation reduction reaction;
(2) oxidative regeneration process of reduction-state oxygen carrier or metal sulfide, make air, oxygen enrichment or purity oxygen enter in the 2nd described burning chemistry chains reactor by described air, oxygen enrichment or purity oxygen pipeline, react with reduction-state oxygen carrier or metal sulfide generation oxidation regeneration;
(3) handoff procedure of burning chemistry chains reactor, harmful components concentration in the product of the reduction reaction in the 1st burning chemistry chains reactor reaches setting value, when oxygen concentration in the product of the oxidation reaction in the 2nd burning chemistry chains reactor reaches setting value, switch three-way valve, make described dusty gas enter the 2nd described burning chemistry chains reactor, air, oxygen enrichment or purity oxygen enter the 1st described burning chemistry chains reactor.
8. the processing method of dusty gas according to claim 7, is characterized in that:
Also comprise and the described sulfur dioxide capturing device of the sulfur dioxide in the product of described oxidation reaction is trapped.
9. the processing method of dusty gas according to claim 8, is characterized in that:
The temperature of described reduction reaction is 200 DEG C ~ 500 DEG C;
The temperature of described oxidation regeneration reaction is 150 DEG C ~ 500 DEG C.
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| CN106996569A (en) * | 2017-05-24 | 2017-08-01 | 中国东方电气集团有限公司 | A kind of devices and methods therefor for the processing sludge that burnt based on heat accumulating type chemical chain |
| CN109340790A (en) * | 2018-11-30 | 2019-02-15 | 中冶南方工程技术有限公司 | A kind of fuel gas release processing system and method |
| WO2019161776A1 (en) * | 2018-02-24 | 2019-08-29 | 北京联力源科技有限公司 | Fuel chemical looping hydrogen production system and method |
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