CN106890567B - Fluidized bed urea and decomposition and denitration system and process of derivative thereof - Google Patents
Fluidized bed urea and decomposition and denitration system and process of derivative thereof Download PDFInfo
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- CN106890567B CN106890567B CN201710220817.3A CN201710220817A CN106890567B CN 106890567 B CN106890567 B CN 106890567B CN 201710220817 A CN201710220817 A CN 201710220817A CN 106890567 B CN106890567 B CN 106890567B
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000004202 carbamide Substances 0.000 title claims abstract description 83
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims abstract description 27
- 239000003546 flue gas Substances 0.000 claims abstract description 134
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- 239000007789 gas Substances 0.000 claims abstract description 55
- 239000002699 waste material Substances 0.000 claims abstract description 30
- 239000000428 dust Substances 0.000 claims abstract description 23
- 238000005243 fluidization Methods 0.000 claims abstract description 21
- 239000006227 byproduct Substances 0.000 claims abstract description 19
- 239000012495 reaction gas Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 44
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 42
- 239000003345 natural gas Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 13
- 150000003672 ureas Chemical class 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 11
- 230000009471 action Effects 0.000 claims description 9
- 238000004891 communication Methods 0.000 claims description 9
- 230000001502 supplementing effect Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 239000002918 waste heat Substances 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical group 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- 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
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
- B09B3/45—Steam treatment, e.g. supercritical water gasification or oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2067—Urea
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides a fluidized bed urea and a decomposition and denitration system of derivatives thereof, belonging to the technical field of flue gas denitration. The system comprises a fluidized bed reactor, a primary cyclone separator, a secondary cyclone separator, a flue gas and reaction gas mixer, a multi-layer denitration reactor and an air preheater. The fluidized bed reactor is internally provided with a fluidized gas distributor, a fluidized plate, a catalyst bed layer, a gas shielding dust remover and an internal cyclone. The invention also relates to a process for decomposing and denitrating by using the system. The decomposing and denitrating system of the invention utilizes the fluidized bed reactor to decompose the raw materials, and the decomposition rate reaches 95 percent. The raw materials used in the invention are industrial emissions, and the fluidized bed reactor is utilized to decompose urea and derivatives thereof, triamine waste products and NH generated by triamine by-products 3 The flue gas is subjected to denitration, the flue gas provides a fluidization medium for the fluidized bed reactor, and meanwhile, the recycling of urea and triamine waste products and the flue gas is realized, so that the waste treatment and denitration cost is reduced, and the environmental pollution is reduced.
Description
Technical Field
The invention belongs to the technical field of flue gas denitration, and particularly relates to a fluidized bed urea and a decomposition and denitration system and process of derivatives thereof.
Background
With the improvement of national environmental protection indexes, the control of the fume emission indexes of the boilers of the coal-fired power plants is more and more strict, and the emission of fume pollutants of the coal-fired power plants is widely focused by the world and society. The invention of the flue gas denitration technology of the selective catalytic reduction is widely popularized in the whole country, so that liquid ammonia, ammonia water and urea are widely used as flue gas denitration reducing agents.
1. Liquid ammonia denitration technology
The liquid ammonia denitration is a selective catalytic reduction flue gas denitration technology, and adopts a vertical catalyst reaction towerRemoving nitrogen oxides (NOx) from flue gas with anhydrous liquid ammonia, mixing ammonia gas as reactant with flue gas, passing through catalyst bed layer, and selectively reducing NOx to N under the action of catalyst 2 And H 2 O; the selection of the denitration reducing agent is mainly from the safety and economical aspects. In recent years, as the use and transportation permission of liquid ammonia are more and more difficult to obtain from local management departments, the safety precaution requirements are more and more stringent, and the corresponding safety cost is more and more high, so that ammonia water and urea are more and more used as denitration reducing agents.
2. Ammonia water denitration technology
The ammonia water denitration is to gasify 20% -30% ammonia water solution by a specially manufactured ammonia water evaporator, then mix the gasified ammonia water solution with air with a certain proportion, and then spray the ammonia water solution into the flue gas by an ammonia spraying grating plate to complete the denitration reduction reaction.
3. Urea pyrolysis technology
The urea pyrolysis reaction process is that high concentration urea solution is sprayed into a pyrolysis furnace, and liquid drops are evaporated under the condition of hot flue gas with the temperature of 350-650 ℃ to obtain solid or molten urea, and pure urea is decomposed and hydrolyzed under the heating condition to finally generate NH 3 And CO 2 ，NH 3 Is fed into a reactor as a denitration reducing agent and selectively reduces NOx into N under the action of a catalyst 2 And H 2 O; the urea pyrolysis technology has the defects of complex equipment manufacture, high energy consumption and the like;
4. urea hydrolysis denitration technology
Preparing granular urea into 40-50% (wt) urea solution, pumping the urea solution into a human hydrolysis heat exchanger, heating to 185 ℃ and then entering a urea hydrolyzer to decompose into NH 3 And CO 2 Then enters a denitration reactor to selectively reduce NOx into N under the action of a catalyst 2 And H 2 O; the urea hydrolysis denitration technology has the defects of higher requirements on the biuret content of urea solution and the like.
5. Wet flue gas denitration technology by urea
The wet flue gas denitration by urea is to spray and absorb NO and NO in flue gas by adopting urea aqueous solution 2 And react with ureaAnd forming nitrogen gas, thereby achieving the aim of flue gas denitration. However, wet oxidation requires the addition of an oxidizing agent to the solution, which can react with urea (reducing agent) in the absorption liquid, resulting in increased consumption of oxidizing agent and urea.
Disclosure of Invention
In order to solve the problems of high safety risks, high raw material and energy consumption, complex equipment manufacturing and the like in the production, storage and transportation of the existing flue gas denitration technology, and simultaneously solve the problem of difficult recycling of waste substances (such as waste triamine and triamine by-products) generated in the production of urea and triamine, the waste materials generated in the production of urea and triamine are fully utilized, the pollution to the environment is reduced, and the operation cost of flue gas treatment is reduced. The invention provides a method for preparing urea and derivatives thereof, and waste substances (such as waste triamine and triamine by-products) generated in the production of triamine, which are used as raw materials and decomposed to generate NH 3 And CO 2 The decomposed gas is used for denitrating the flue gas under the action of a denitration catalyst to remove nitrogen oxides in the flue gas, so that the purposes of denitration, purification and evacuation of the flue gas are achieved. The aim of the invention is achieved by the following technical scheme:
a fluidized bed urea and its derivative decomposing and denitrating system comprises a fluidized bed reactor, a primary cyclone separator, a secondary cyclone separator, a flue gas and reaction gas mixer, a multi-layer denitrating reactor and an air preheater which are sequentially connected in series.
As an embodiment of the fluidized bed urea and its derivative decomposing and denitrating system, the system further comprises a Roots blower I connected and communicated with the air preheater.
As a specific embodiment of the fluidized bed urea and the decomposition and denitration system of the derivative thereof, the system further comprises a feeding tank connected and communicated with the lower part of the fluidized bed reactor, and a bucket elevator connected and communicated with the feeding tank.
As a concrete example of the decomposing and denitrating system for the fluidized bed urea and the derivative thereof, a spray gun is arranged at the joint of the lower part of the fluidized bed reactor and the charging tank.
As a specific embodiment of the fluidized bed urea and the decomposition and denitration system of the derivative thereof, the cyclone dipleg of the primary cyclone separator is communicated with the upper part of the fluidized bed reactor.
As a specific embodiment of the fluidized bed urea and derivative decomposition and denitration system, the system further comprises a dust discharge tank which is connected and communicated with the secondary cyclone separator.
As a specific embodiment of the decomposing and denitrating system for the fluidized bed urea and the derivative thereof, the fluidized bed reactor is internally provided with a fluidized gas distributor, a fluidized plate, a catalyst bed layer, a gas shielding dust remover and an internal cyclone.
As a specific example of the decomposition and denitration system of the fluidized bed urea and the derivative thereof, the fluidized bed reactor is filled with one or two of SiO2 or Al2O3 catalysts; the temperature of the fluidized bed reactor is 200-350 ℃ and the pressure is 0.05-0.15 MPa.
As a specific embodiment of the fluidized bed urea and derivative decomposition and denitration system, the system further comprises a flue gas fan, a hot blast stove and a Roots blower II which are sequentially connected and communicated with the bottom of the fluidized bed reactor.
As a concrete embodiment of the fluidized bed urea and the decomposition and denitration system of the derivative thereof, the flue gas fan is communicated with the bottom of the fluidized bed reactor through a flue gas inlet pipeline.
As a specific embodiment of the fluidized bed urea and its derivative decomposing and denitrating system, the flue gas inlet pipeline is provided with a steam supplementing pipeline.
As a specific embodiment of the fluidized bed urea and the decomposition and denitration system of the derivative thereof, the hot blast stove adopts natural gas for heating.
As a specific example of the decomposition and denitration system of the fluidized bed urea and the derivative thereof, the temperature of the fluidized bed reactor is controlled by adjusting the natural gas amount entering the hot blast stove.
As a concrete example of the decomposing and denitrating system of the fluidized bed urea and the derivative thereof, the hot blast stove is connected and communicated with a flue gas pipeline; and a flow regulating valve is arranged between the hot blast stove and the flue gas pipeline.
As a specific embodiment of the fluidized bed urea and the decomposition and denitration system of the derivative thereof, the hot blast stove is connected and communicated with the air preheater.
As a specific embodiment of the fluidized bed urea and the decomposition and denitration system of the derivative thereof, the flue gas and reaction gas mixer is connected and communicated with a flue gas pipeline.
The invention also provides a process for flue gas denitration by utilizing the fluidized bed urea and derivative decomposition and denitration system thereof, which comprises the following steps:
(1) Lifting urea derivatives, triamine waste products or triamine by a bucket elevator into a feeding tank, then entering the lower part of the fluidized bed reactor through a material inlet pipeline, and spraying the urea derivatives, the triamine waste products or the triamine by a spray gun into the bed layer of the fluidized bed reactor;
(2) The flue gas from the flue gas pipeline is heated by the hot blast stove, boosted by the flue gas fan, and then enters the fluidized bed reactor through the flue gas inlet pipeline together with low-pressure water vapor from the vapor supplementing pipeline, and the bed temperature of the fluidized bed reactor is raised to the temperature required by material decomposition; simultaneously, flue gas is uniformly distributed through a fluidization gas distributor and a fluidization plate in the fluidized bed reactor, so that the catalyst in the bed layer of the fluidized bed reactor is in a fluidization state from bottom to top;
(3) Urea derivative, triamine waste or triamine by-product decomposed into NH under the conditions of steam, fluidized catalyst, reaction temperature and pressure 3 And CO 2 ；
(4) The gas flow from the top of the fluidized bed reactor enters a primary cyclone separator, and the catalyst separated by the primary cyclone separator returns to the fluidized bed reactor through a cyclone dipleg;
(5) The gas from the top of the primary cyclone separator enters the secondary cyclone separator, and the rest catalyst dust is discharged into a dust discharge tank through a cyclone dipleg of the secondary cyclone separator;
(6) The gas coming out from the top of the secondary cyclone separator enters a mixer of the flue gas and the reactor and is mixed with a large amount of flue gas from a flue gas pipeline;
(7) Mixed gas from the flue gas and reaction gas mixer enters from the top of the multi-layer denitration reactor, and nitrogen oxides and NH in the flue gas under the action of the denitration catalyst 3 Reduction reaction to N 2 And H 2 O；
(8) And (3) recycling waste heat from the gas discharged from the bottom of the multi-layer denitration reactor through an air preheater and then emptying.
As a specific example of the fluidized bed urea and its derivative decomposition and denitration process of the present invention, the process further comprises: air is compressed and boosted by the Roots blower I, enters an air preheater, exchanges heat with gas exhausted from the bottom of the multi-layer denitration reactor, and enters the hot blast stove after being heated, so as to provide air required by natural gas combustion.
As a specific example of the fluidized bed urea and the decomposition and denitration process of the derivative thereof, the temperature of the flue gas heated by the hot blast stove is 250-400 ℃, and the pressure boosted by the flue gas fan is 0.1-0.2 MPa.
As a specific example of the decomposition and denitration process of the fluidized-bed urea and its derivatives according to the present invention, the low-pressure water vapor has a pressure of 0.1 to 0.2MPa, and the low-pressure water vapor is added in such an amount that the gas stream exiting from the top of the fluidized-bed reactor does not contain H 2 O is the same as or equal to.
As a specific example of the decomposition and denitration process of the fluidized-bed urea and the derivative thereof, the gas flow coming out from the top of the fluidized-bed reactor is NH 3 、CO 2 Smoke and a small amount of catalyst.
As a specific example of the fluidized bed urea and the decomposition and denitration process of the derivative thereof, the denitration catalyst is a metal oxide denitration catalyst.
The invention also provides an application of the fluidized bed urea and the decomposition and denitration system and process of the fluidized bed urea and the derivative thereof, and the application of the system and process in the decomposition and denitration of urea and the derivative thereof, triamine waste products and triamine by-products.
The invention has the beneficial effects that:
1. the decomposition and denitration system of the invention utilizes the fluidized bed reactor to decompose urea and derivatives thereof, triamine waste products and triamine by-products, the decomposition effect is higher, the decomposition rate is more sufficient, and the decomposition rate can reach more than 95 percent;
2. the raw materials used in the fluidized bed reactor of the invention are urea and the industrial wastes such as derivatives, triamine waste products, triamine by-products and the like, and the raw materials are decomposed into NH required by denitration 3 The cost required by denitration is reduced, and meanwhile, the waste is fully utilized, so that the environmental pollution is reduced;
3. the fluidized bed reactor adopts the flue gas as a fluidization medium, and partial nitrogen oxides in the flue gas participate in the denitration reaction in the fluidized bed, so that the water vapor amount required by the decomposition reaction of waste materials can be lower than expected, and the load of the denitration reactor is reduced;
4. the raw materials used in the fluidized bed reactor and the multi-layer denitration reactor are industrial emissions, and NH generated by decomposing industrial wastes by using the fluidized bed reactor 3 The flue gas is subjected to denitration in the multi-layer denitration reactor, meanwhile, the flue gas provides a fluidization medium for the fluidized bed reactor, all links are mutually matched, recycling of urea, triamine waste products and the flue gas is realized, waste treatment and denitration cost is reduced, and environmental pollution is reduced.
5. The existing urea generally adopts a thermal decomposition technology, the temperature of a thermal decomposition chamber is 350-650 ℃, and a large amount of high-temperature air (the temperature is about 650 ℃) is consumed, so that the urea belongs to a high-temperature condition, and the energy consumption is relatively high; the temperature of the fluidized bed reactor is only 200-350 ℃ and the pressure is 0.05-0.15 MPa. Compared with the prior art, the method adopts the fluidized bed reactor to decompose urea and derivatives thereof, triamine waste products and triamine by-products, has lower requirements on temperature and pressure and lower energy consumption.
Drawings
FIG. 1 is a schematic diagram of a fluidized bed urea and derivative decomposition and denitration system according to the present invention;
FIG. 2 is a schematic view of the structure of the fluidized bed reactor according to the present invention;
reference numerals: 1-fluidized bed reactor, 2-first cyclone separator, 3-second cyclone separator, 4-flue gas and reaction gas mixer, 5-multi-layer denitration reactor, 6-air preheater, 7-Roots blower I, 8-charging tank, 9-bucket elevator, 101-spray gun, 201-cyclone dipleg, 10-dust discharging tank, 102-fluidized gas distributor, 103-fluidization plate, 104-gas dust remover, 105-inner cyclone, 106-flue gas inlet pipe, 107-end enclosure, 108-catalyst bed layer, 109-discharge pipe, 11-flue gas blower, 12-hot blast stove, 13-Roots blower II, 14-flue gas inlet pipe, 15-steam supplementing pipe, 16-flue gas pipe and 17-flow regulating valve.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
A fluidized bed urea and its derivative decomposing and denitrating system is shown in figure 1. The system comprises a fluidized bed reactor 1, a primary cyclone separator 2, a secondary cyclone separator 3, a flue gas and reaction gas mixer 4, a multi-layer denitration reactor 5 and an air preheater 6 which are sequentially connected in series. In the system of the invention, a fluidized bed reactor 1 is used for decomposing urea and derivatives thereof, triamine waste products and triamine by-products, and a primary cyclone separator 2 is used for separating the gas stream (containing NH) from the top of the fluidized bed reactor 3 、CO 2 The flue gas and a small amount of catalyst) and the secondary cyclone 3 is used for further separating the catalyst in the gas stream and discharging the catalyst out of the system; the flue gas and reaction gas mixer 4 is used for mixing the flue gas and the reaction gas, and then enters the multi-layer denitration reactor 5 for denitration reaction, so that nitrogen oxides (NOx) in the flue gas and the nitrogen oxides (NOx) in the flue gas are mixedNH 3 Reduction reaction to N 2 And H 2 The air preheater 6 heats air by utilizing the heat of the gas after the denitration reaction, and introduces the heated air into the hot blast stove 12 to serve as air required by natural gas combustion, so that the purposes of saving energy and reducing consumption are further achieved.
Further, the system includes a Roots blower I7 in communication with the air preheater 6. The Roots blower I7 is used for compressing air, boosting the pressure of sucked air, and then entering the air preheater 6 for heat exchange and then entering the hot blast stove 12 to provide air required by natural gas combustion.
In order to facilitate the addition of urea and derivatives thereof, waste triamines and by-products of triamines, the system of the invention further comprises a feed tank 8 in communication with the lower portion of the fluidized bed reactor 1, and a bucket elevator 9 in communication with the feed tank. Furthermore, a spray gun 101 is arranged at the joint of the lower part of the fluidized bed reactor 1 and the charging tank 8, and the spray gun 101 can spray decomposed raw materials onto the fluidized bed of the fluidized bed reactor, so that the reaction materials are fully contacted with the catalyst distributed on the fluidized bed, the reaction efficiency is improved, and the decomposition is more complete.
Further, the cyclone dipleg 201 of the primary cyclone 2 is connected to communicate with the upper portion of the fluidized bed reactor 1. The purpose of this arrangement is to return the catalyst collected by the primary cyclone 2 to the fluidized bed reactor, thereby saving the catalyst usage.
The gas discharged from the top of the primary cyclone separator 2 also contains some catalyst dust which is too fine in particle size, and the raw material fed into the fluidized bed reactor 1 contains a certain amount of solid dust which needs to be discharged out of the system periodically, a secondary cyclone separator 3 for further recovering the catalyst dust is arranged behind the primary cyclone separator 2, and the catalyst dust is discharged into a dust discharge tank 10 through a material leg of the secondary cyclone separator 3 and then is discharged into a dust storage tank or is used as waste residue to be packaged through the dust discharge tank 10.
The fluidized bed reactor 1 is internally provided with a fluidized gas distributor 102, a fluidized plate 103, a catalyst bed 108, a gas-blocking dust remover 104 and an internal cyclone 105, and the structure of the fluidized gas distributor is shown in figure 2. A gas-blocking dust remover 104 is arranged at the upper part of the fluidized bed reactor 1 to primarily separate the gas flow from the catalyst in the reactor; the top internal wind 105 will further separate the gas stream from the catalyst. The fluidized bed reactor is adopted to decompose urea and derivatives thereof, triamine waste products and triamine by-products, the decomposition rate can reach more than 95 percent, and compared with the prior thermal decomposition, the fluidized bed reactor has lower temperature and pressure and lower energy consumption. The fluidized bed reactor 1 of the invention has the following specific process for decomposing urea and derivatives, triamine waste products and triamine by-products:
flue gas enters the fluidization gas distributor 102 through the flue gas inlet pipe 106, then enters the cavity of the fluidized bed seal head 107, passes through the two layers of fluidization plates 103 after the seal head 107 is filled with air flow, and after passing through the fluidization plates 103, the fluidization gas is redistributed, so that the gas flow and the flow velocity distribution on the same section of the reactor are more uniform. The flue gas fluidization gas flowing from bottom to top in the catalyst bed 108 drives the catalyst to move together with urea and urea derivatives atomized by the spray gun 101, the movement speed between ions is increased due to the stirring action between the air flow and the catalyst in the movement, the probability of contact collision between the ions is increased, the urea or urea derivatives gasified by heating in the collision contact with water vapor added in the flue gas flows at a high speed under the action of heat energy and the catalyst to form a surge state, the heat and mass transfer efficiency is improved, and the hydrolysis reaction of urea and the urea derivatives in the reaction bed and the water vapor is completed rapidly. The reaction is as follows
CO(NH 2 ) 2 +H 2 O→2NH 3 +CO 2 (hydrolysis of urea)
Urea derivatives (such as melamine and its by-products) are also susceptible to hydrolysis with water under heating to form cyanuric acid (C) 3 H 3 O 3 N 3 ) And ammonia is released, while cyanuric acid is easy to depolymerize when heated to generate cyanuric acid (CHNO), and the cyanuric acid is unstable in property and easy to hydrolyze to generate ammonia and carbon dioxide.
C 3 N 6 H 6 +3H 2 O→C 3 H 3 O 3 N 3 +3NH 3 (triamine hydrolysis)
C 3 H 3 O 3 N 3 3CHNO (cyanuric acid depolymerized by heating)
CHNO+H 2 O→NH 3 +CO 2 (cyanic acid hydrolysis)
The reaction gas from the catalyst bed continues to flow down and up through the gas trap 104, with the entrained catalyst portion of the gas stream being separated. The gas flow continues to flow upwards along the reactor into the inner cyclone 105 after passing through the gas-blocking dust remover 104, and is discharged out of the reactor through the discharge pipe 109 into the primary cyclone 2 after the final separation of the reaction gas flow and the entrained catalyst is completed.
In order to make more complete use of the decomposition of urea and its derivatives, waste triamine products and by-products, and to increase the decomposition rate, the fluidized bed reactor 1 is filled with SiO 2 Or Al 2 O 3 One or two of the catalysts; the temperature of the fluidized bed reactor is 200-350 ℃ and the pressure is 0.05-0.15 MPa. The catalyst used for decomposing urea and its derivatives in the fluidized bed reactor of the present invention may be any catalyst other than the catalyst disclosed in the present invention as long as it can decompose urea and its derivatives.
Further, the decomposing and denitrating system also comprises a flue gas fan 11, a hot blast stove 12 and a Roots blower II 13 which are sequentially connected and communicated with the bottom of the fluidized bed reactor 1 and are used for providing flue gas for decomposing the raw materials of the fluidized bed reactor 1 to fluidize the catalyst. The flue gas fan 11 boosts the pressure of the flue gas and is used as fluidization flue gas for decomposing raw materials, so that the catalyst forms a fluidization state; the hot blast stove 12 is used for heating the flue gas, and the temperature of the fluidized bed layer is increased along with the heat brought into the fluidized bed reactor 1 by the flue gas to reach the temperature required by the catalyst decomposition reaction, so that the reaction raw materials are decomposed into NH required by denitration 3 The method comprises the steps of carrying out a first treatment on the surface of the The Roots blower II sucks air to boost pressure, and provides the air required by natural gas combustion of the hot blast stove 12, so that the flue gas in the hot blast stove 12 is heated.
The flue gas in the fluidized bed reactor acts as a fluidizing medium for flowing the catalyst; the high-temperature flue gas fluidizes the catalyst and enables the flow of the reactor to form a surge state, and in the surge state, the high-temperature flue gas gives off heat and drives the catalyst and material particles in the bed to move vigorously, so that the materials are fully mixed and mutually contacted and collided, the heat and mass transfer between the materials is accelerated, and the reaction speed and the reaction efficiency are improved.
The flue gas fan 11 is connected and communicated with the bottom of the fluidized bed reactor 1 through a flue gas inlet pipeline 14. Further, a steam supplementing pipe 15 is provided on the flue gas inlet pipe 14. Before the fluidized flue gas enters the fluidized bed reactor 1, a certain amount of water vapor required for decomposing urea derivatives, triamine waste products, triamine by-products and the like is added, so a vapor supplementing pipeline 15 is arranged on the flue gas inlet pipeline 14. The steam supplement amount on the flue gas inlet pipeline 12 is determined by the material decomposition amount in the fluidized bed reactor 1 and the content of nitrogen oxides in the flue gas, and in order to ensure higher reaction efficiency in the multi-layer denitration reactor, the steam supplement amount in the fluidized bed reactor should be basically free of H in the gas flow flowing out of the fluidized bed reactor 1 2 O is the same as or equal to. The invention is provided with the water vapor supplementing amount of the fluidized bed reactor to control H in the outlet gas of the reactor 2 O content. When the amount of water vapor added into the reactor is too high, the moisture content in the outlet gas of the reactor is too high, and the existence of excessive moisture can influence the denitration reaction in the subsequent process, because the flue gas denitration finally generates H 2 O；
4NH 3 +4NO+O 2 →4N 2 +6H 2 O
In contrast, when the amount of steam fed into the reactor is too low, the urea and derivative decomposition reaction proceeds incompletely, resulting in a decrease in reaction efficiency.
Specifically, the invention uses natural gas to heat the stove 12. The flue gas in the hot blast stove 12 is heated by the heat generated by the combustion of the natural gas and then enters the fluidized bed reactor 1, so that the temperature of the fluidized bed reactor 1 is controlled by adjusting the natural gas quantity entering the hot blast stove 12, the more the natural gas quantity is, the more the heat generated by the combustion is, the higher the flue gas temperature is, the more the same amount of flue gas is brought into the fluidized bed reactor 1, and the higher the reactor temperature is.
The concrete process of controlling the temperature of the reactor by the natural gas amount comprises the following steps: when the deviation is generated between the measured temperature value and the set value, the temperature controller outputs a signal to adjust the opening of the natural gas valve of the hot blast stove so as to input a certain amount of natural gas, synchronously adjust the opening of the air door of the hot blast stove, and proportion the air inlet amount of a certain proportion so as to meet the oxygen amount required by the full combustion of the natural gas of the hot blast stove. When the measured temperature of the reactor is lower than a set value, the regulator outputs a signal to increase the opening of a natural gas valve and an air throttle which enter the hot blast stove, and increase the natural gas and the air quantity, so that more combustion heat is obtained to increase the temperature of the flue gas at the outlet of the hot blast stove, and the heat brought into the reactor is increased to finally increase the temperature of the reactor; when the measured temperature of the reactor is higher than the set value, the regulator outputs a signal to reduce the opening of the natural gas valve and the air throttle which enter the hot blast stove, so that the natural gas and the air quantity which enter the hot blast stove are reduced, namely the combustion heat of the hot blast stove is reduced, the outlet temperature of the hot blast stove is reduced, and the reduction of the heat brought into the reactor finally reduces the temperature of the reactor.
In order to ensure that the flue gas required by the decomposition reaction of the fluidized bed reactor 1 is provided, the hot blast stove 12 is connected and communicated with a flue gas pipeline 16; meanwhile, a flow regulating valve 17 is arranged between the hot blast stove 12 and the flue gas pipeline 16.
Further, the hot blast stove 12 is connected and communicated with the air preheater 6. The purpose of setting like this is to let in hot-blast furnace 12 with the air after the heat transfer of air heater 6, as the required air of natural gas burning, further realizes heat recovery, reduces and shoutes, practices thrift the cost.
In order to ensure the smooth proceeding of the flue gas denitration reaction, the flue gas and reaction gas mixer 4 is connected and communicated with the flue gas pipeline 16. The flue gas and reaction gas mixer 4 provides a place for mixing the flue gas and the reaction gas, and the flue gas and the reaction gas are converged and then introduced into the multi-layer denitration reactor 5 for denitration reaction.
The invention relates to a process for flue gas denitration by a fluidized bed urea and derivative decomposition and denitration system thereof, which comprises the following steps:
(1) The urea derivative, the triamine waste or the triamine by-product is lifted by a bucket elevator 9 to enter a charging tank 8, then enters the lower part of the fluidized bed reactor 1 through a material inlet pipeline, and is sprayed into the bed layer of the fluidized bed reactor 1 through a spray gun 101;
(2) The flue gas from the flue gas pipeline is heated by a hot blast stove 12, boosted by a flue gas fan 11, and then enters the fluidized bed reactor 1 through a flue gas inlet pipeline 14 together with low-pressure water vapor from a vapor supplementing pipeline 15, and the bed temperature of the fluidized bed reactor 1 is raised to the temperature required by material decomposition; simultaneously, the flue gas is uniformly distributed through a fluidization gas distributor 102 and a fluidization plate 103 in the fluidized bed reactor 1, so that the catalyst in the bed layer of the fluidized bed reactor 1 is in a fluidization state from bottom to top;
(3) Urea derivative, triamine waste or triamine by-product decomposed into NH under the conditions of steam, fluidized catalyst, reaction temperature and pressure 3 And CO 2 ；
(4) The gas flow from the top of the fluidized bed reactor 1 enters the primary cyclone separator 2, and the catalyst separated by the primary cyclone separator 2 returns to the fluidized bed reactor 1 through the cyclone dipleg 201;
(5) The gas from the top of the primary cyclone separator 2 enters the secondary cyclone separator 3, and the rest catalyst dust is discharged into a dust discharge tank 10 through cyclone diplegs of the secondary cyclone separator 3;
(6) The gas coming out from the top of the secondary cyclone separator 3 enters a flue gas and reactor mixer 4 and is mixed with a large amount of flue gas from a flue gas pipeline 16;
(7) The mixed gas from the flue gas and reaction gas mixer 4 enters from the top of the multi-layer denitration reactor 5, and nitrogen oxides and NH in the flue gas under the action of the denitration catalyst 3 Reduction reaction to N 2 And H 2 O；
(8) The gas discharged from the bottom of the multi-layer denitration reactor 5 is discharged after waste heat is recovered by the air preheater 6.
Further, to achieve the recycling of the system heat, the process further comprises: air is compressed and boosted by the Roots blower I, enters an air preheater, exchanges heat with gas exhausted from the bottom of the multi-layer denitration reactor, and enters the hot blast stove after being heated, so as to provide air required by natural gas combustion.
In the decomposition and denitration process of the invention, the required amount and temperature of the flue gas depend on the flow rate of the reactor and the temperature required by the decomposition reaction of the fluidized bed reactor. Preferably, the temperature of the flue gas heated by the hot blast stove is 250-400 ℃, and the pressure boosted by the flue gas fan is 0.1-0.2 MPa.
The pressure of the low-pressure water vapor is 0.1-0.2MPa, the pressure is consistent with the pressure of the flue gas fluidization gas of the reactor to be 0.1-0.2MPa, and the main function of the water vapor is to help urea and derivatives thereof to decompose.
The steam is added in such an amount that the gas stream exiting from the top of the fluidized-bed reactor is free of H 2 O is the same as or equal to. The water vapor supplement amount is determined by the material decomposition amount in the fluidized bed reactor 1 and the content of nitrogen oxides in the flue gas, and in order to ensure higher reaction efficiency in the multi-layer denitration reactor 5, the water vapor supplement amount in the fluidized bed reactor should be basically free of H in the gas flow flowing out of the fluidized bed reactor 1 2 O is the same as or equal to.
Further, the gas flow coming out from the top of the fluidized bed reactor 1 is NH 3 、CO 2 Smoke and a small amount of catalyst.
Further, the denitration catalyst is a conventional denitration catalyst such as a metal oxide denitration catalyst, and the denitration temperature is a conventional denitration control temperature. The denitration catalyst and the temperature are all conventional in the field, and the denitration catalyst and the temperature can be realized only by the catalyst and the temperature.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (6)
1. The fluidized bed urea and its derivative decomposing and denitrating process includes the following steps: 1) The urea derivative, the triamine waste or the triamine byproduct is lifted by a bucket elevator to enter a feeding tank, then enters the lower part of the fluidized bed reactor through a material inlet pipeline, and is sprayed into the bed layer of the fluidized bed reactor through a spray gun;
2) The flue gas from the flue gas pipeline is heated by the hot blast stove, boosted by the flue gas fan, and then enters the fluidized bed reactor through the flue gas inlet pipeline together with low-pressure water vapor from the vapor supplementing pipeline, and the bed temperature of the fluidized bed reactor is raised to the temperature required by material decomposition; simultaneously, flue gas is uniformly distributed through a fluidization gas distributor and a fluidization plate in the fluidized bed reactor, so that the catalyst in the bed layer of the fluidized bed reactor is in a fluidization state from bottom to top;
3) Urea derivatives, triamine waste products or triamine byproducts are decomposed into NH under the conditions of water vapor, fluidized catalyst, reaction temperature and pressure 3 And CO 2 ；
4) The gas flow from the top of the fluidized bed reactor enters a primary cyclone separator, and the catalyst separated by the primary cyclone separator returns to the fluidized bed reactor through a cyclone dipleg;
5) The gas from the top of the primary cyclone separator enters the secondary cyclone separator, and the rest catalyst dust is discharged into a dust discharge tank through a cyclone dipleg of the secondary cyclone separator;
6) The gas coming out from the top of the secondary cyclone separator enters a mixer of the flue gas and the reactor and is mixed with a large amount of flue gas from a flue gas pipeline;
7) Mixed gas from the flue gas and reaction gas mixer enters from the top of the multi-layer denitration reactor, and nitrogen oxides and NH in the flue gas under the action of the denitration catalyst 3 Reduction reaction to N 2 And H 2 O；
8) The gas exhausted from the bottom of the multi-layer denitration reactor is exhausted after waste heat is recovered by an air preheater;
the fluidized bed reactor is filled with SiO 2 Or Al 2 O 3 One or two of the catalysts; the temperature of the fluidized bed reactor is 200-350 ℃ and the pressure is 0.05-0.15 MPa; the temperature of the flue gas heated by the hot blast stove is 250-400 ℃, and the pressure of the flue gas boosted by the flue gas fan is 0.1-0.2 MPa; the pressure of the low-pressure water vapor is 0.1-0.2MPa, and the low-pressure water vapor is added in an amount that the gas flow from the top of the fluidized bed reactor does not contain H 2 O is the same as or equal to.
2. A fluidized bed urea and derivative decomposition and denitration process according to claim 1, wherein said process further comprises: air is compressed and boosted by the Roots blower I, enters an air preheater, exchanges heat with gas exhausted from the bottom of the multi-layer denitration reactor, and enters the hot blast stove after being heated, so as to provide air required by natural gas combustion.
3. The fluidized bed urea and its derivative decomposing and denitrating process as claimed in claim 1, wherein a fluidized bed urea and its derivative decomposing and denitrating system is adopted in the process, and the system comprises a fluidized bed reactor, a primary cyclone separator, a secondary cyclone separator, a flue gas and reaction gas mixer, a multi-layer denitrating reactor and an air preheater which are sequentially connected in series; the fluidized bed reactor is internally provided with a fluidized gas distributor, a fluidized plate, a catalyst bed layer, a gas shielding dust remover and an internal cyclone.
4. A process for the decomposition and denitration of fluidized bed urea and its derivatives as claimed in claim 3, wherein said system further comprises a roots blower i in communication with the air preheater, a dust discharge tank in communication with the secondary cyclone, a feed tank in communication with the lower portion of the fluidized bed reactor, and a bucket elevator in communication with the feed tank.
5. A process for the decomposition and denitration of urea and its derivatives in a fluidized bed as claimed in claim 3, wherein said system further comprises a flue gas fan, a hot blast stove and a Roots blower ii connected in sequence with the bottom of said fluidized bed reactor; the flue gas fan is connected and communicated with the bottom of the fluidized bed reactor through a flue gas inlet pipeline, and a steam supplementing pipeline is arranged on the flue gas inlet pipeline; the hot blast stove is connected and communicated with the air preheater, and the hot blast stove adopts natural gas for heating.
6. A process for the decomposition and denitration of urea and its derivatives in accordance with claim 3, wherein said flue gas and reaction gas mixer is in communication with a flue gas duct, said hot blast stove is in communication with the flue gas duct, and a flow control valve is provided between the hot blast stove and the flue gas duct.
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