CN108176224A - A kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method and device - Google Patents
A kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method and device Download PDFInfo
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- CN108176224A CN108176224A CN201810057884.2A CN201810057884A CN108176224A CN 108176224 A CN108176224 A CN 108176224A CN 201810057884 A CN201810057884 A CN 201810057884A CN 108176224 A CN108176224 A CN 108176224A
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- ammonia
- flue gas
- denitration
- catalytic cracking
- desulfurization
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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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
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
A kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method, including step：The catalyst regeneration flue gas for high temperature dirt containing catalyst that catalytic cracking unit comes initially enters waste heat boiler I, and flue-gas temperature drops to 280 430 DEG C；Flue gas heat is generated by waste heat boiler I and is supplied outside steam；280 430 DEG C of flue gas enters denitrification apparatus denitration, enters waste heat boiler II by exhaust pass after fully being reacted on denitrating catalyst surface in Benitration reactor；Using ammonia as reactant, sulfur dioxide, nitrogen oxides and the producing ammonium sulfate byproduct in flue gas are removed, while removes the catalyst dust in regenerated flue gas, clean gas qualified discharge, the purification method of three-waste free discharge, the catalyst regeneration smoke gas treatment of the catalytic cracking applied to oil refining.
Description
Related application
It is on May 20th, 2015 that the application, which is the applying date, and application No. is 201510261073.0 applications for a patent for invention " one
The divisional application of kind regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method and device ".
Technical field
The invention belongs to field of environment protection, are related to oil refining industry regeneration fume from catalytic cracking sulfur dioxide, nitrogen oxygen
Compound, the process and device of dirt control.
Background technology
Catalytic cracking is secondary operation important in oil refining process, is to improve yield of light oil, produces high-knock rating gasoline,
While the and important means of high-yield diesel oil.Catalytically cracked material is heavy distillate and heavy oil (normal slag subtracts slag), wherein containing compared with
The nonhydrocarbons such as more sulphur, nitrogen, oxygen, these nonhydrocarbon elements and heavy metal element, transfer in process of production product, catalyst,
In industrial wastewater, some is discharged into flue gas and catalyst dust in ambient enviroment, is polluted.
The catalyst of catalytic cracking burns the regenerated flue gas of generation, enters cyclone separator through regenerator dilute phase section, through two
Grade cyclone separator separates most of catalyst of carrying, and regenerated flue gas temperature is very high and contains about 5%~10%CO, in order to
Using its heat, many devices are equipped with CO boilers, and water vapour is generated using regenerated flue gas.For the higher device of operating pressure,
It is standing to have smoke energy recovering system, using the thermal energy of regenerated flue gas and pressure work done, main air blower is driven to save electric energy.
For Petrochemical Enterprises, regeneration fume from catalytic cracking is the largest air pollution source, mainly contains CO, SOx、NOx
Etc. harmful components and catalyst dust particle, SO2、NOx, dirt be Air Pollutant Discharge, be the important pollution sources for causing haze.
Especially SOxAnd NOx, with air quality in flue gas emission to air, is seriously affected, can also corrosion be generated to device, influence device
Normal operation, therefore regenerated flue gas is treated as major tasks very important in environment protection treating.
Regeneration fume from catalytic cracking usually has the characteristics that：General 800 DEG C of temperature or more；Concentration containing SOx, NOx
It will height compared to other industry；Dirt：30-800mg/m3, SOx：100-1500mg/m3, NOx：100-1200mg/m3.Dirt is usually to contain
Al2O3Deng catalyst granules.Reduce SO in regeneration fume from catalytic crackingxAnd NOxThere are three approach for concentration：(1) catalysis is reduced to split
Change raw material sulphur, nitrogen content；(2) using transfer catalyst；(3) flue gas desulfurization and denitrification.Reduce catalytically cracked material sulphur nitrogen content
Method is fcc raw material weighted BMO spaces, and fcc raw material sulfur content can be made to drop to less than 0.3%, but invests high, construction 3,100,000
The ton pre- hydrogenation plant of fcc raw material about needs 1,200,000,000 yuan of investment.The transfer catalyst technology country has developed for many years, individually using this skill
Art is difficult to make neat stress up to standard.
Regeneration fume from catalytic cracking sulfur method mainly has sodium method, calcium method, there is high investment, operating cost height, discharges and give up
The deficiencies of water.
Control NO in regeneration fume from catalytic crackingxThe technology of content mainly selective catalytic reduction method (SCR), selectivity
Noncatalytic reduction (SNCR), liquid absorption method, solid absorption method, high energy electron active oxidation method etc..
CN201410590103 discloses a kind of catalytic cracking flue gas desulfurization and dust collecting process, catalytic cracking flue gas pass through successively
Three technical process of flue gas ash removal and first desulfurization, flue gas desulfurization and flue gas degassing sol is crossed, catalysis is split by power wave apparatus
Change flue gas and carry out purification and washing, flue gas, by spray washing and mechanical demisting, realizes wet desulphurization and dehumidifying, finally on absorption tower
Electric defogging method is crossed, droplet is trapped by electrion, makes dustiness≤30mg/Nm in flue gas3, reach flue gas emission mark
It is accurate.Using sodium alkali sulfur method, remove the sulfur dioxide in oil plant catalytic cracking flue gas and remove the height carried secretly in flue gas
Concentration catalyst dust.
CN201320319032 discloses a kind of catalytic cracking flue gas desulfurating dust-removing equipment, including Multi-layer sprinkling absorber portion and
Rinse-system imports desulfurizing agent by two absorbent imports on desulfation tower.Flue gas enters desulfurization by gas inlet
It is acidified in tower, desulfurization and dedusting is carried out by desulfurizing agent of NaOH solution, and pass through the liquid that spray-absorption section removes entrained in flue gas
Drop, has the function that purifying smoke.
CN201210108141 discloses a kind of method of regeneration fume from catalytic cracking denitration purification；In the constant temperature zone of reactor
It is middle filling two catalyst beds, epimere be the first catalyst bed, hypomere be the second catalyst bed, centre be not provided with every
Layer, regeneration fume from catalytic cracking is from lower into the catalyst bed of reactor and temperature reaction；First catalyst and the second catalysis
The mass ratio of agent is 1: 1-10；First catalyst is nano Ce O2Support the catalyst of perovskite composite oxides, the second catalysis
Agent is the molecular sieve of skeleton containing transition metal, and the second catalyst contains auxiliary agent；Perovskite composite oxides are in nano Ce O2On
Load capacity be 10-50wt%；The amount ratio of the substance of transition metal and auxiliary agent is 0.1-0.3；The sial of HZSM-5 molecular sieves rubs
, than being 25-100, the loading of transition metal over a molecular sieve is 0.05-6wt% for you；
The present invention provides a kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting integral technology and devices, can make
The SO of regeneration fume from catalytic cracking discharge2Control is in 35mg/Nm3Below, NOxControl is in 40mg/Nm3Below, dirt control is in 5mg/
Nm3Below.The present invention realizes the dust removal integrated control of desulphurization denitration, more conventional independent desulphurization and denitration, dedusting technology section
More than 30% is about invested, saves more than 20% operating cost, there is apparent technology and application advantage.
Invention content
The present invention seeks to propose a kind of regeneration fume from catalytic cracking desulphurization denitration dedusting one based on ammonia process of desulfurization denitration
Body technology and device, so as to fulfill the high-efficient purification of regeneration fume from catalytic cracking.And technological process is simple, easy to operate, dress
Put it is stable, avoid have technique some shortcomings.
The technical scheme is that：A kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method, feature exist
In including the following steps：
1) the catalyst regeneration flue gas for high temperature dirt containing catalyst that catalytic cracking unit comes initially enters waste heat boiler I, cigarette
Temperature degree drops to 280-430 DEG C；Flue gas heat is generated by waste heat boiler I and is supplied outside steam；
2) 280-430 DEG C of flue gas enters denitrification apparatus, includes denitration inlet flue duct, spray ammonia successively by flow of flue gas direction
Mixed-rectification system, Benitration reactor, denitrating catalyst and exhaust pass；Enter denitration import quoted from the flue gas of waste heat boiler I
It is mixed at spray ammonia with ammonia after flue, Benitration reactor is entered after spraying ammonia mixed-rectification system rectification, in denitration
Waste heat boiler II is entered by exhaust pass after fully being reacted on denitrating catalyst surface in reactor；
3) flue gas is reduced to 80-220 DEG C through waste heat boiler II temperature, and flue gas heat is generated by waste heat boiler II outside steam
For；
4) 80-220 DEG C of flue gas enters desulfurization dust-removal system, and absorb oxysulfide with the circulating absorption solution containing ammonia washs simultaneously
Catalyst dirt, absorbing liquid parameter are adjusted according to oxysulfide removing amount, sulfoxide concentration, and treated, and clean pneumatic transmission chimney is arranged
It puts；
5) ammonium sulfate that desulfurization dust-removal system generates send ammonium sulfate processing system, concentrated, crystallization, separation of solid and liquid, drying,
It is packaged to be outside solid ammonium sulfate product and supplies；
6) the gentle ammonia generator of ammonia storage tank is generally comprised for ammonia system.Gas ammonia generator includes ammonia evaporator, ammonia buffers
Tank, dilution air and ammonia-air mixer.Ammonia enters ammonia surge tank after ammonia evaporator evaporates, the sky come with dilution air
Gas is mixed in ammonia-air mixer, and the ammonia after dilution enters flue gas system by ammonia spraying and mixing system and carries out denitration.
An ammonia part send desulfurization dust-removal system to make desulphurization reaction agent.
7) 80-220 DEG C of flue gas enters desulfurization dust-removal system, absorbs oxysulfide washing catalyst simultaneously with circulating absorption solution
Dirt, absorbing liquid parameter are adjusted according to oxysulfide removing amount, sulfoxide concentration, and treated, and clean 45-65 DEG C of temperature degree is sent
Smoke stack emission；The ammonium sulfate that desulfurization dust-removal system generates send ammonium sulfate processing system, concentrated, crystallization, separation of solid and liquid, drying,
It is packaged to be outside solid ammonium sulfate product and supplies；It is responsible for denitration, the storage of desulphurization reaction agent, configuration and supply for ammonia system.
According to the above method, device proposed by the present invention：Successively include waste heat boiler I, denitrification apparatus, waste heat boiler II and
Desulfurization dust-removal system, the denitrification apparatus include successively by flow of flue gas direction denitration inlet flue duct, spray ammonia mixed-rectification system,
Benitration reactor, denitrating catalyst and exhaust pass；Ammonia is supplied to spray ammonia mixed-rectification system and desulfurization dust-removal system for ammonia system,
Flue gas from waste heat boiler I is mixed after entering denitration inlet flue duct at spray ammonia with ammonia, by spraying ammonia mixed-rectification
Enter Benitration reactor, exhaust pass after system rectification；Include the gentle ammonia generator of ammonia storage tank for ammonia system.
Gas ammonia generator includes ammonia evaporator, ammonia surge tank, dilution air and ammonia-air mixer.Ammonia is evaporated through ammonia
Enter ammonia surge tank after device evaporation, the air come with dilution air is mixed in ammonia-air mixer, the ammonia after dilution
Gas enters flue gas system by ammonia spraying and mixing system and carries out denitration；An ammonia part send desulfurization dust-removal system to make desulphurization reaction agent.
800 DEG C of temperature of the regenerated flue gas of catalytic cracking handled for the present invention or more；Particulate matter：30-800mg/m3,
SOx：100-1500mg/m3, NOx：100-1200mg/m3。
Processing method proposed by the present invention, denitration efficiency >=85% after regeneration fume from catalytic cracking purification, desulfuration efficiency
98%, neat stress NOxLess than 50mg/Nm3、SO2Less than 35mg/Nm3, dirt be less than 20mg/Nm3, byproduct of ammonium sulfate, clean gas reaches
Mark discharge, while invest that low, technological process is simple, operating cost is low.
Beneficial effects of the present invention：The present invention is a kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting integral skill
Art and device, desulphurization denitration high dust collection efficiency, three-waste free discharge, non-secondary pollution, complete resource.The technology of the present invention advantage exists
In realizing high-efficiency desulfurization denitration dust collecting with relatively low investment and operating cost, it is ensured that clean gas qualified discharge can meet environmentally friendly height
The requirement of standard.Technological process is simple, easy to operate, and device is stable.Inventive desulfurization, denitration are all produced with a set of ammonia system
Raw ammonia is reactant, reduces operation, the maintenance work of desulphurization and denitration.Cigarette is made using flue gas and waste-heat recovery device
Desulfurization and denitration carry out at best temperature, are conducive to higher desulphurization and denitration efficiency.By being recycled to flue gas heat
It utilizes.
Description of the drawings
Fig. 1 is a kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting integral technology and device flow diagram.
Specific embodiment
1000000 tons of catalytic cracking unit catalyst regeneration flue gases, exhaust gas volumn 135000Nm3/ h, 950 DEG C of temperature, water 12%,
Nitrogen oxides 360mg/Nm3, sulfur dioxide 2300mg/Nm3, dirt 150mg/Nm3.Desulfurizing agent is 99.6% liquefied ammonia.
1) flue gas that catalytic cracking unit comes initially enters waste heat boiler I, and flue-gas temperature drops to 310-350 DEG C；Flue gas heat
Amount is generated by waste heat boiler I and is supplied outside steam.
2) 310-350 DEG C of flue gas enters denitrification apparatus, includes inlet flue duct, spray ammonia mixing successively by flow of flue gas direction
Commutation system, Benitration reactor, denitrating catalyst and exhaust pass.Quoted from waste heat boiler flue gas enter denitration flue after spraying
It is mixed at ammonia with ammonia, Benitration reactor is entered after over commutation, pass through outlet after catalyst surface fully reacts
Flue removes waste heat boiler II.
3) flue gas is reduced to 115-145 DEG C through waste heat boiler II temperature, and flue gas heat is generated by waste heat boiler II outside steam
For.
4) 115-145 DEG C of flue gas enters desulfurization dust-removal system, and absorb oxysulfide with circulating absorption solution washs catalysis simultaneously
Agent dirt, absorbing liquid parameter are adjusted according to oxysulfide removing amount, sulfoxide concentration, clean pneumatic transmission smoke stack emission that treated；
5) ammonium sulfate that desulfurization dust-removal system generates send ammonium sulfate processing system, concentrated, crystallization, separation of solid and liquid, drying,
It is packaged to be solid ammonium sulfate international sale；
6) the gentle ammonia generator of ammonia storage tank is generally comprised for ammonia system.Gas ammonia generator includes ammonia evaporator, ammonia buffers
Tank, dilution air and ammonia-air mixer.Ammonia enters ammonia surge tank after ammonia evaporator evaporates, the sky come with dilution air
Gas is mixed in ammonia-air mixer, and the ammonia after dilution enters flue gas system by ammonia spraying and mixing system and carries out denitration.
An ammonia part send desulfurization dust-removal system to make desulphurization reaction agent.
Effect：Denitration efficiency >=88.9%, desulfuration efficiency 98.5%, neat stress NOx38mg/Nm3、SO232mg/Nm3, dirt
Less than 15mg/Nm3, byproduct of ammonium sulfate nitrogen content 20.8%.
Desulfurization dust-removal system is conventional equipment, including desulfurized dust collection column, circulating pump (can be integrated with desulfurized dust collection column), is followed
The equipment such as annular groove, oxidation fan, settling tank, filter.In short, rear road ammonia process of desulfurization flow and device are not directed to content using existing
There are public technology or the authorized ammonia desulfuration equipment series of patents of applicant.As CN200510040801.1,
CN03158258.3, CN201010275966.8, CN200510040800.7, CN03158257.5 etc..Catalyst use with
TiO2For base material, with V2O5For main active ingredient, with WO3、MoO3For anti-oxidant, antitoxinization auxiliary ingredients.Catalyst pattern can
It is divided into three kinds：Board-like, cellular and corrugated plate dst.
Particular embodiments described above has carried out the purpose of the present invention, technical solution and advantageous effect further in detail
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention
Within the scope of shield.
Claims (14)
- A kind of 1. regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method, it is characterised in that：80-220 DEG C of flue gas enters de- Sulphur dust pelletizing system absorbs oxysulfide washing catalyst dirt simultaneously with the circulating absorption solution of ammonification, and absorbing liquid parameter is according to sulphur oxygen Compound removing amount, sulfoxide concentration adjustment, treated, and clean 45-65 DEG C of temperature degree send smoke stack emission；The ammonium sulfate that desulfurization dust-removal system generates send ammonium sulfate processing system；Wherein, the particle concentration of the regenerated flue gas of catalytic cracking：30-800mg/m3。
- 2. the method as described in claim 1, which is characterized in thatThe catalyst regeneration flue gas for high temperature dirt containing catalyst that catalytic cracking unit comes initially enters waste heat boiler I, flue-gas temperature Drop to 280-430 DEG C；Flue gas heat is generated by waste heat boiler I and is supplied outside steam；280-430 DEG C of flue gas enters denitrification apparatus, whole including denitration inlet flue duct, spray ammonia mixing successively by flow of flue gas direction Streaming system, Benitration reactor, denitrating catalyst and exhaust pass.
- 3. method as claimed in claim 2, which is characterized in that the flue gas after denitration is sent into waste heat boiler II；More than flue gas warp Heat boiler II temperature is reduced to 80-220 DEG C, and flue gas heat is generated by waste heat boiler II and supplied outside steam.
- 4. method as claimed in claim 2, which is characterized in that 800 DEG C of temperature of the regenerated flue gas of catalytic cracking or more；SOx： 100-1500mg/m3, particle concentration：30-800mg/m3, NOx：100-1200mg/m3。
- 5. the method as described in claim 1, which is characterized in that ammonium sulfate that desulfurization dust-removal system generates is concentrated, crystallization, solid Liquid separation, is packaged to be confession outside solid ammonium sulfate product at drying.
- 6. regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method according to claim 2, it is characterised in that：By remaining Flue-gas temperature is dropped to 310-350 DEG C by heat boiler I；310-350 DEG C of flue gas enters denitrification apparatus.
- 7. regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method according to claim 3, which is characterized in that waste heat Flue-gas temperature is reduced to 115-145 DEG C and enters desulfurization dust-removal system by boiler II.
- 8. regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method according to claim 2, which is characterized in that catalysis Denitration efficiency >=85% after the purification of cracking regenerated flue gas, neat stress NOxLess than 50mg/Nm3、SO2Less than 35mg/Nm3, dirt is less than 20mg/Nm3。
- 9. method as claimed in claim 2, which is characterized in that denitrating catalyst is used with TiO2For base material, with V2O5It is main Active ingredient, with WO3、MoO3For anti-oxidant, antitoxinization auxiliary ingredients.
- 10. method as claimed in claim 9, which is characterized in that denitrating catalyst pattern can be divided into three kinds：It is board-like, cellular And corrugated plate dst.
- 11. a kind of device of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting, which is characterized in that including waste heat boiler I, take off Nitre device, desulfurization dust-removal system, ammonium sulfate processing system.
- 12. device as claimed in claim 11, which is characterized in that the ammonia that denitrification apparatus is needed with desulfurization dust-removal system is by supplying ammonia System provides, and is responsible for denitration, the storage of desulphurization reaction agent, configuration and supply for ammonia system, including the gentle ammonia generator of ammonia storage tank； Gas ammonia generator includes ammonia evaporator, ammonia surge tank, dilution air and ammonia-air mixer；The ammonia of ammonia storage tank is evaporated through ammonia Enter ammonia surge tank after device evaporation, the air come with dilution air is mixed in ammonia-air mixer, the ammonia after dilution Gas enters flue gas system by ammonia spraying and mixing system and carries out denitration；An ammonia part send desulfurization dust-removal system as desulphurization reaction agent.
- 13. device as claimed in claim 11, which is characterized in that desulfurization dust-removal system includes desulfurized dust collection column, circulating pump, follows The equipment such as annular groove, oxidation fan, settling tank, filter.
- 14. regeneration fume from catalytic cracking ammonia process of desulfurization denitrification apparatus according to claim 13, it is characterised in that：Device packet Include waste heat boiler I, denitrification apparatus, waste heat boiler II, desulfurization dust-removal system, ammonium sulfate processing system, for ammonia system, the denitration Device is included denitration inlet flue duct, spray ammonia mixed-rectification system, Benitration reactor, denitration catalyst by flow of flue gas direction successively Agent and exhaust pass；For ammonia system to spray ammonia mixed-rectification system and desulfurization dust-removal system for ammonia, the flue gas from waste heat boiler I It is mixed at spray ammonia with ammonia after into denitration inlet flue duct, it is anti-that denitration is entered after spraying ammonia mixed-rectification system rectification Answer device, exhaust pass；Include the gentle ammonia generator of ammonia storage tank for ammonia system.
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| CN201510261073.0A CN104941423B (en) | 2015-05-20 | 2015-05-20 | A kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method and device |
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| CN104941423A (en) | 2015-09-30 |
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