CN109499357A - A kind of method of nitrous oxide emission in improvement commercial plant - Google Patents
A kind of method of nitrous oxide emission in improvement commercial plant Download PDFInfo
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- CN109499357A CN109499357A CN201811518230.1A CN201811518230A CN109499357A CN 109499357 A CN109499357 A CN 109499357A CN 201811518230 A CN201811518230 A CN 201811518230A CN 109499357 A CN109499357 A CN 109499357A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/869—Multiple step processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8631—Processes characterised by a specific device
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/11—Air
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
- B01D2255/9022—Two layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/402—Dinitrogen oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/30—Improvements relating to adipic acid or caprolactam production
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Abstract
The invention discloses a kind of method of nitrous oxide emission in improvement commercial plant, this method is nitrous oxide emission reduction catalyst to be loaded on the platinum catalyst bottom bracket that design has " spider web " shape, by N based on nitric acid oxidation furnace basic device2O is converted into N2And O2、NO2And NO, the improvement of catalysis and the nitrous oxide emission reduction of process gas is realized in set of device.Present invention process is simple, and investment is small, and operation, maintenance cost are lower, has wide applicability, can be used for many industrial source N2The emission reduction process (such as nitric acid production, adipic acid produce process) of O, has a extensive future.
Description
Technical field
The invention discloses a kind of methods of nitrous oxide emission in improvement commercial plant, belong to chemical production technical neck
Domain.
Background technique
6 kinds of greenhouse gases of prescribed requirement emission reduction in United Nations Framework Convention on Climate Change and " Paris weather summit "
Are as follows: carbon dioxide (CO2), methane (CH4), nitrous oxide (N2O), hydrofluorocarbons (HFCs), perfluorocarbon compound
(PFCs), sulfur hexafluoride (SF6).Nitrous oxide gas has a major impact global climate and atmospheric chemistry process.Equal substances
The greenhouse effects of amount nitrous oxide are 200 ~ 300 times of carbon dioxide.Meanwhile photochemical product NO can be with O in stratosphere3
Reaction destroys atmospheric ozone layer (Crutzen, 1970).Nitrous oxide concentration is just with annual 0.25% or so speed in atmosphere
Increase, the every increase 5ppb of atmospheric oxidn Asia nitrogen partial pressure, corresponding Radiative Forcing increases by 11%.Research shows that nitrous oxide (N2O) it is
Toxic and harmful gas, toxicity sustainable 15 years as long as, N2The GWP(global greenhouse effect of O) it is same concentration C O2310 times, often
The lower Nature comparison of temperature is stablized, and can be analyzed to nitrogen and oxygen under high temperature.National Environmental Protection Agency there is no mandatory requirement and discharge at present
Standard.
Nitric acid is the basic material of chemical industry.China is large agricultural country, and the demand dosage created to nitric acid is very huge
Greatly.Using ammonia as raw material, in the reaction process through platinum catalyst catalysis ammonia production nitric acid, nitrous oxide emission must be generated.Oxygen
Changing sub- nitrogen is that ammoxidation prepares NO in nitric acid production2Byproduct (2NH3+2O2=N2O+3H2O), yield is generally dependent on instead
Answer pressure, the temperature (200 ~ 250 DEG C) of furnace.Pressure is different, N2The production rate of O is also different.Nitric acid is produced after ammonia catalytic
Mixed gas in the general nitrous oxide for all containing 1100 ~ 1800ppm, the nitrous oxide of such high concentration must handle；And
One medium-sized or above nitric acid production enterprise, air speed cross ten thousand, and the amount for being thrown into the nitrous oxide in atmosphere per hour is huge, without
The nitrous oxide emission of processing certainly will poison the body of the mankind into atmosphere, pollute atmosphere, adverse condition.
Nitrous oxide emission reduction has 4 kinds of approach, first is that other products (such as phenol) are produced using nitrous oxide, second is that by oxygen
Change sub- nitrogen high temp to decompose, third is that by nitrous oxide selective catalytic reduction (SCR), fourth is that nitrous oxide is directly catalytically decomposed.
Wherein, nitrous oxide is directly catalytically decomposed has the advantages that at low cost, simple process, decomposition efficiency is high, therefore has good
Industrial applications prospect." summary of nitrous oxide emission reduction CDM project operation " (Zhang Yanli；Bright Setsuka；Li Hongzheng；Jinan, Shandong Province
Sheng Yuan chemical fertilizer Co., Ltd, chemical fertilizer industry, the 6th phase in 2012, P67-68) describe Sheng Yuan company using Switzerland tie up it is more
The nitrous oxide catalyst of company, the loading catalyst in the oxidation furnace of dilute nitric acid production device pass through a platinum catalyst week
Phase operation, nitrous oxide emission reduction efficiency is 85% or more.
It is all catalyst detection emission reduction effect on laboratory installation either mini-pilot plant that the country is reported at present
Fruit there is no mature technology technology, and the case being especially applied successfully on commercial plant, this severely limits nitrous oxide emission reductions
The development of technology.
Summary of the invention
For above situation, the purpose of the present invention is to provide one kind to realize improvement oxidation on a set of nitric acid industry device
Sub- nitrogen discharged method.
Second object of the present invention is to provide a kind of new process for realizing nitrous oxide emission reduction without new device.
Third object of the present invention is to provide a kind of improvement expenses low, the simple emission reduction catalyst support of technology
Frame.
Fourth object of the present invention is to provide a kind of activity stability height, the good catalyst of anti-ammonia ability.
5th purpose of the invention can original of the by-product a part as nitric acid production during being nitrous oxide emission reduction
Material.
To achieve the goals above, the present invention is based on nitric acid oxidation furnace basic devices, have the platinum of " spider web " shape to urge in design
Nitrous oxide emission reduction catalyst is loaded on agent bottom bracket, by N2O is converted into N2And O2、NO2And NO, it is realized in set of device
The improvement of catalysis and the nitrous oxide emission reduction of process gas.Present invention process is simple, and investment is small, and operation, maintenance cost are lower, has
Wide applicability can be used for many industrial source N2The emission reduction process (such as nitric acid production, adipic acid produce process) of O, prospect
It is wide.Specific embodiment provided by the invention is as follows:
The method of nitrous oxide emission, includes the following steps: in a kind of improvement commercial plant
(1) air is passed through ammonia sky mixer by, is passed through oxidation furnace entrance after then being mixed gas ammonia after filtering decompression,
Enter in oxidation furnace after to dedusting；
(2) ammonia catalytic reaction is completed under acts on ammonia sky gaseous mixture through platinum catalyst in oxidation furnace, subsequent gas passes through again
Peroxidating Asia nitrogen emission reduction catalyst removes the nitrous oxide in gaseous mixture；
(3) process gas is generated after reaction, enters useless pot after leaving emission reduction catalyst and desalted water exchanges heat, the process gas for the pot that gives up out
After cooling, enters nitrogen oxide gas compressor together with the auxiliary air filled into and compressed.
Further, the gas ammonia pressure is 40 ~ 60KPa, and air/gas ammonia ratio is 9.5 ~ 12.5.
Further, in the step (2) oxidation furnace temperature be 800 DEG C ~ 850 DEG C, pressure be -0.4KPa ~ -
0.2KPa, leading to ammonia amount is 2000 ~ 3000m3/ h, air speed are 20000 ~ 30000h-1。
Further, the nitrous oxide catalyst specification is 10 ~ 13mm × 12 ~ 15mm and 10 ~ 16mm × 15 Φ ~ 20mm
Honeycomb cylindrical body；Relative density is 0.7 ~ 0.9, and active temperature is 600 DEG C ~ 1100 DEG C.
A kind of to realize the device for administering the method for nitrous oxide emission in commercial plant, which includes oxidation furnace (2), oxygen
Change furnace (2) upper and lower ends and be respectively arranged with oxidation furnace entrance (1) and oxidation outlet of still (6), oxidation furnace is internally provided with N2O emission reduction
Structure, the gas ammonia are passed through after oxidation furnace entrance (1) by N2O emission reduction structure, to after reaction again by oxidation outlet of still (6)
Discharge.
Further, the N2O emission reduction structure is by platinum catalyst (3), nitrous oxide emission reduction catalyst (4) from top to bottom
It is formed with nitrous oxide emission reduction catalyst bracket.
Further, the platinum catalyst (3) and N2The height of O emission reduction catalyst bracket (5) is 0.1 ~ 0.25m, diameter
For 1.5 ~ 3.0m.
What platinum catalyst of the present invention and emission reduction catalyst bracket were selected is that patent publication No. is CN101423202B
The converter for ammonia oxidation being made of platinum guaze bracket both catalyst basket and its support construction in technical solution.
What nitrous oxide emission reduction catalyst of the present invention was selected is a kind of processing of Publication No. CN103586040B
N2The catalyst of O and its technical solution in preparation process.
The beneficial effects of the present invention are:
1. the present invention provides a kind of new methods that can administer nitrous oxide emission on a set of nitric acid industry device.Unstripped gas exists
While catalysis by platinum catalyst, and nitrous oxide is administered through nitrous oxide emission reduction catalyst, it is sub- to have saved newly-built oxidation
The investment of nitrogen exhaust gas processing device.For investing little nitric acid enterprise, the present invention has good economic technique superiority.
2. a further advantage is that used novel platinum catalyst is independently to know with emission reduction catalyst bracket
The advantages of knowing property right (patent No.: ZL 200810182558.0), combining own device, manufacture difficulty simple using structure
Small novel platinum catalyst bracket makes the optimum for being in horizontal plane in platinum catalyst and catalyst operation, invests small, reduction
The system shutdown repair time.
3. a further advantage is that used catalyst is to possess the nitrous oxide of independent intellectual property right to subtract
It arranges catalyst (patent No.: ZL 201310582549.1), at 840 DEG C, leads to ammonia amount about 2700m3Under/h, the thermostabilization of catalyst
Property, anti-ammonia are good；Shape is butterfly end socket, avoid the gaseous mixture that is come by platinum catalyst cannot with catalyst high-efficient contact,
The problems such as forming catalyst bridging.After emission reduction catalyst, N in nitric acid tail gas discharge2The content of O is no more than 50ppm, emission reduction
Efficiency is up to 95% or more.
4. a further advantage is that having led to system resistance drop after having loaded nitrous oxide emission reduction catalyst
Increase, but by subsequent operation, reduce secondary air flow, oxidation furnace pressure requirements can be reached by increasing primary air flow, no
The operation for influencing the oxidation furnace and its apparatus system of micro-negative pressure operation, ensure that the yield of dust technology and concentrated nitric acid.
5. meeting yet another advantage of the present invention is that can be used as the raw material of nitric acid production in emission reduction byproduct in process part
" green manufacturing, energy-saving and emission-reduction " developing direction.
Detailed description of the invention
Fig. 1 is to install N in oxidation furnace2O emission reduction structural schematic diagram；
In figure: 1 is oxidation furnace entrance, and 2 be oxidation furnace, and 3 be platinum catalyst, and 4 be nitrous oxide emission reduction catalyst, and 5 be N2O emission reduction
Catalyst bracket, 6 be oxidation outlet of still.
Specific embodiment
In the following with reference to the drawings and specific embodiments to nitrous oxide emission in a kind of improvement commercial plant provided by the invention
Method be described in detail.
Embodiment 1
Comparative example: certain nitric plant's device aoxidizes 835 DEG C ~ 855 DEG C of in-furnace temperature, and ventilate ammonia amount about 2700m3/ h, wherein oxidation is sub-
Nitrogen content are as follows: 800 ~ 1000ppm.
Using traditional treatment method: National Environmental Protection Agency there is no mandatory requirement and discharge standard at present, direct emission or
Newly-built device for absorbing tail gas is handled.
Administer the nitrous oxide using the method for the present invention: air removes dust and sundries by air purifier, into ammonia
Empty mixer is mixed after filtering and decompression with the gas ammonia from freezing work number, and oxidation furnace 2(is entered after mixing dust removing and is tied
It closes shown in Fig. 1).It is air speed 24000h in service condition-1, tiny structure -0.31KPa, 840 DEG C of in-furnace temperature, ammonia flow is about
2700m3/ h, after 3 catalyst of platinum catalyst, the nitrous oxide of generation about 990ppm ~ 1100ppm, using nitrous oxide
Emission reduction catalyst 4 is catalyzed, and is laminated difference < 100Pa, and system pressure is without obviously increasing, device normal operation.Cycle of operation total duration
It 1200 hours, is sampled in tail gas unit, through analyzing, nitrous oxide is 50 ~ 60ppm.Catalyst Conversion is up to 95% or more.
Embodiment 2
Comparative example: certain nitric plant's device aoxidizes 835 DEG C ~ 855 DEG C of in-furnace temperature, and ventilate ammonia amount about 2700m3/ h, wherein oxidation is sub-
Nitrogen content are as follows: 800 ~ 1000ppm.
Using traditional treatment method: National Environmental Protection Agency there is no mandatory requirement and discharge standard at present, direct emission or
Newly-built device for absorbing tail gas is handled.
Administer the nitrous oxide using the method for the present invention: air removes dust and sundries by air purifier, into ammonia
Empty mixer is mixed after filtering and decompression with the gas ammonia from freezing work number, and oxidation furnace is entered after mixing dust removing.?
Service condition is air speed 27000h-1, tiny structure -0.28KPa, 845 DEG C of in-furnace temperature, ammonia flow is about 2800m3/ h, by platinum
After catalyst agent, the nitrous oxide of generation about 1000ppm ~ 1100ppm, using nitrous oxide emission reduction catalyst,
Bed pressure difference < 100Pa, system pressure is without obviously increasing, device normal operation.Cycle of operation total duration 1000 hours, in tail gas
It is sampled on device, through analyzing, nitrous oxide content is 25 ~ 35ppm.Catalyst Conversion is up to 96.8% or more.
Embodiment 3
Comparative example: certain nitric plant's device aoxidizes 825 DEG C ~ 855 DEG C of in-furnace temperature, and ventilate ammonia amount about 2700m3/ h, wherein oxidation is sub-
Nitrogen content are as follows: 800 ~ 1000ppm.
Using traditional treatment method: National Environmental Protection Agency there is no mandatory requirement and discharge standard at present, direct emission or
Newly-built device for absorbing tail gas is handled.
Administer the nitrous oxide using the method for the present invention: air removes dust and sundries by air purifier, into ammonia
Empty mixer is mixed after filtering and decompression with the gas ammonia from freezing work number, and oxidation furnace is entered after mixing dust removing.?
Service condition is air speed 24000h-1, tiny structure -0.31KPa, 825 DEG C of in-furnace temperature, ammonia flow is about 2700m3/ h, by platinum
After catalyst agent, the nitrous oxide of generation about 990ppm ~ 1100ppm, using nitrous oxide emission reduction catalyst, bed
It is laminated difference < 100Pa, system pressure is without obviously increasing, device normal operation.It cycle of operation total duration 1000 hours, is filled in tail gas
Sampling is set, through analyzing, nitrous oxide is 150 ~ 165ppm.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (7)
1. a kind of method for administering nitrous oxide emission in commercial plant, which is characterized in that this method comprises the following steps:
(1) air is passed through ammonia sky mixer by, is passed through oxidation furnace entrance after then being mixed gas ammonia after filtering decompression,
Enter in oxidation furnace after to dedusting；
(2) ammonia catalytic reaction is completed under acts on ammonia sky gaseous mixture through platinum catalyst in oxidation furnace, subsequent gas passes through again
Peroxidating Asia nitrogen emission reduction catalyst removes the nitrous oxide in gaseous mixture；
(3) process gas is generated after reaction, enters useless pot after leaving emission reduction catalyst and desalted water exchanges heat, the process gas for the pot that gives up out
After cooling, enters nitrogen oxide gas compressor together with the auxiliary air filled into and compressed.
2. method according to claim 1, which is characterized in that the air is the air after dedusting and sundries, the gas
Ammonia pressure is 40 ~ 60KPa, and air/gas ammonia ratio is 9.5 ~ 12.5.
3. method according to claim 1, which is characterized in that the temperature of oxidation furnace is 800 DEG C ~ 850 in the step (2)
DEG C, pressure is -0.4KPa ~ -0.2KPa, and leading to ammonia amount is 2000 ~ 3000m3/h, and air speed is 20000 ~ 30000h-1。
4. method according to claim 1, which is characterized in that the nitrous oxide catalyst specification be 10 ~ 13mm × 12 ~
15mm and 10 ~ 16mm × 15 Φ ~ 20mm honeycomb cylindrical body；Relative density is 0.7 ~ 0.9, and active temperature is 600 DEG C ~ 1100
℃。
5. a kind of realize the device as described in claim 1 for administering the method for nitrous oxide emission in commercial plant, the device
Including oxidation furnace (2), oxidation furnace (2) upper and lower ends are respectively arranged with oxidation furnace entrance (1) and oxidation outlet of still (6), feature
It is, oxidation furnace is internally provided with N2O emission reduction structure, the gas ammonia are passed through after oxidation furnace entrance (1) by N2O emission reduction structure, to
It is discharged again by oxidation outlet of still (6) after reaction.
6. device according to claim 5, which is characterized in that the N2O emission reduction structure is by platinum catalyst from top to bottom
(3), nitrous oxide emission reduction catalyst (4) and nitrous oxide emission reduction catalyst bracket composition.
7. device according to claim 5, which is characterized in that the platinum catalyst (3) and N2O emission reduction catalyst bracket (5)
Height be 0.1 ~ 0.25m, diameter be 1.5 ~ 3.0m.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023006867A1 (en) * | 2021-07-28 | 2023-02-02 | Basf Se | New geometry for den2o catalyst |
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