CN106807201A - A kind of denitration method for flue gas of coproduction cyanuric acid - Google Patents
A kind of denitration method for flue gas of coproduction cyanuric acid Download PDFInfo
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- CN106807201A CN106807201A CN201710066660.3A CN201710066660A CN106807201A CN 106807201 A CN106807201 A CN 106807201A CN 201710066660 A CN201710066660 A CN 201710066660A CN 106807201 A CN106807201 A CN 106807201A
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- denitration
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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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/32—Cyanuric acid; Isocyanuric acid
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Abstract
The present invention relates to a kind of denitration method for flue gas of coproduction cyanuric acid, belong to gas cleaning processing technology field.Denitration method for flue gas of the invention, comprises the following steps：Urea condensation reacts, and the ammonia of generation is passed through formalin, is reacted, and the material that the reaction is obtained carries out denitration as denitrfying agent injection denitration reaction area under 500 1100 DEG C of temperature conditionss.The present invention obtains cyanuric acid and liquid denitrfying agent with urea and formaldehyde as raw material by two-step reaction；Then denitration is carried out using liquid denitrfying agent.Urea and formaldehyde are conventional industrial chemicals, cheap, and transport is in the absence of danger, and cost of transportation is low.Cyanuric acid is obtained while denitrfying agent is prepared, cyanuric acid is widely used industrial chemicals.The present invention obtains the two-step reaction of liquid denitrfying agent, is simple reaction, can be completed using microwave reactor and circulating pump.
Description
Technical field
The present invention relates to a kind of denitration method for flue gas of coproduction cyanuric acid, belong to gas cleaning processing technology field.
Technical background
With China's expanding economy, the environmental pollution that mass energy consumption brings is increasingly serious.China is used as with coal
It is the country of main energy sources, the harmful substance such as contained sulfur dioxide, nitrogen oxides severe contamination air in coal-fired flue-gas, aggravation
Haze weather.Nitrogen oxide emission in strict control flue gas is extremely urgent, finds more economical feasible denitrating flue gas skill
Art also more shows important.
Traditional denitration technology is selective catalytic reduction reaction technology（SCR）With SNCR reaction technology
（SNCR）.Wherein, there is the shortcomings of initial outlay is high, smoke components influence is big, operating cost is high in SCR technology；SNCR technologies are deposited
Reducing agent with flue gas mixability is poor, denitration efficiency is low, ammonia escaped quantity greatly, high energy consumption the shortcomings of.
Largely using ammonia, the main source of ammonia has liquefied ammonia, ammoniacal liquor and urea to existing denitration technology.Wherein, liquefied ammonia and dense
Ammoniacal liquor of the degree more than 8% is harmful influence, and transporting hasardous are high, and freight charges are high；Energy wave in ammoniacal liquor and aqueous solution of urea gasification
Take serious, and denitration efficiency itself is low, ammonia escaped quantity is big；Three is not preferable denitrfying agent.
The content of the invention
For the above-mentioned deficiency of existing denitration technology, the present invention provides a kind of coproduction trimerization with urea and formaldehyde as raw material
The denitration method for flue gas of cyanic acid.
Technical scheme
A kind of denitration method for flue gas of coproduction cyanuric acid, comprises the following steps：
（1）Urea carries out condensation reaction under the conditions of 200-260 DEG C；Condensation reaction generates cyanuric acid solid；
（2）The ammonia of condensation reaction generation is passed through formalin, is reacted；
（3）Step（2）The reaction mass for obtaining enters as denitrfying agent injection denitration reaction area under 500-1100 DEG C of temperature conditionss
Row denitration；
Urea is 1-1.5 with the mol ratio of formaldehyde in formalin：1.
Above-mentioned denitration method for flue gas, the preferably reaction temperature of urea, 220 DEG C.
Above-mentioned denitration method for flue gas, step（2）The reaction mass for obtaining is liquid, and main component is hexa；
The present invention is using the liquid material as denitrfying agent；In order to ensure to need guarantee to be passed through first without formaldehyde, the present invention in the denitrfying agent
Ammonia excess in aldehyde solution, makes the ph values of the reaction mass for finally giving between 11-12, therefore hexa liquid
Contain ammoniacal liquor in denitrfying agent, ammoniacal liquor can improve denitration rate with the common denitration of hexa.But the ammoniacal liquor category of 8% concentrations above
In hazardous chemical, it is stored and is required；The mol ratio of formaldehyde in urea and formalin is defined to 1-1.5 by the present invention：
1.Preferably, urea and the mol ratio of formaldehyde in formalin are 1.08-1.35：1.It is furthermore preferred that in urea and formalin
The mol ratio of formaldehyde is 1.35：1.
The present invention obtains cyanuric acid and liquid denitrfying agent with urea and formaldehyde as raw material by two-step reaction；Then
Denitration is carried out using liquid denitrfying agent.Urea and formaldehyde are conventional industrial chemicals, cheap, and transport is in the absence of danger
Property, cost of transportation is low.Cyanuric acid is obtained while denitrfying agent is prepared, cyanuric acid is widely used industrial chemicals.
The present invention obtains the two-step reaction of liquid denitrfying agent, is simple reaction, can be completed using microwave reactor and circulating pump.This
The used denitration device of invention, can be transformed in the carrying out in the case that boiler or kiln do not stop production, and normal production fortune is not influenceed
OK, easily realize.The present invention prepares the two-step reaction of liquid denitrfying agent, and the product of first step reaction a, part is used for second step
Reaction a, part is cyanuric acid；Second step reacts, and whole materials are used as denitrfying agent in reaction system；There is no waste material to produce.This
Invention is low with scr methods specific investment and operating cost, higher than denitration efficiency with sncr methods, and extra acquisition cyanuric acid is this valuable
The chemical products of value.
Above-mentioned denitration method for flue gas, it is preferred that step（3）" the step（2）The reaction mass for obtaining is noted as denitrfying agent
Enter denitration reaction area " injection pressure be 500-1000kpa.
Above-mentioned denitration method for flue gas, it is preferred that step（3）Temperature conditionss be 900-1100 DEG C.
Above-mentioned denitration method for flue gas, it is preferred that step（3）The reaction time of denitration reaction is 1-5s.
Above-mentioned denitration method for flue gas, it is preferred that NOx in denitrfying agent in hexa and denitration reaction area mole
Than for（0.1-0.8）：1, it is further preferred that hexa is with the mol ratio of NOx（0.2-0.5）：1.The NOx is
Refer to nitrogen oxides.
Beneficial effects of the present invention
1., with urea and formalin as raw material, urea and formalin relative safety are high, and purchase cost is low, no for the present invention
There are transporting hasardous, occupation area of equipment is small；Primary construction cost and later stage operating cost are less than SCR technology；Denitration efficiency
Higher than SNCR technologies, at the same overcome SNCR technologies high energy consumption, the shortcomings of ammonia escaped quantity is big.
2. during denitrfying agent is prepared, urea condensation reaction generates ammonia and cyanuric acid, cyanuric acid to the present invention
Itself it is a kind of chemical products of high added value, with economic benefit.
3. it is of the present invention to carry out the out of stock method of flue gas using urea and formaldehyde joint technology of preparing, it is adaptable to various
Industrial Boiler and Industrial Stoves.
Specific embodiment
With reference to example, the present invention will be further described.
Embodiment 1
850kg urea heats generation ammonia and cyanuric acid under the conditions of 220 DEG C.The ammonia for reacting generation is passed through 1000kg first
Aldehyde solution（Mass concentration is 37%；Similarly hereinafter）In obtain the mixing liquid of hexa and ammoniacal liquor.Using the mixing liquid as
Denitrfying agent is sprayed into pending flue gas, and penetrating pressure is 500kpa, and it is 0.2 with the mol ratio of NOx to control hexa:1,
950 DEG C of maintenance reaction temperature, reacts 2s, and the product that reaction is obtained is N2, CO, CO2, H2O, before detection analysis instrument detection process
The concentration of NOx afterwards, it is 82% to calculate NOx removal efficiency.
Embodiment 2
1000kg urea heats generation ammonia and cyanuric acid under the conditions of 220 DEG C.The ammonia for reacting generation is passed through 1000kg
The mixing liquid of hexa and ammoniacal liquor is obtained in formalin.Pending cigarette is sprayed into using the mixing liquid as denitrfying agent
In gas, penetrating pressure is 500kpa, and it is 0.2 with the mol ratio of NOx to control hexa:1,950 DEG C of maintenance reaction temperature,
Reaction 2s, the product that obtains of reaction is N2, CO, CO2, H2O, with the concentration of NOx before and after detection analysis instrument detection process, is calculated
It is 84% to go out NOx removal efficiency.
Embodiment 3
1100kg urea exists220Generation ammonia and cyanuric acid are heated under the conditions of DEG C.The ammonia for reacting generation is passed through 1000kg
The mixing liquid of hexa and ammoniacal liquor is obtained in formalin.Pending cigarette is sprayed into using the mixing liquid as denitrfying agent
In gas, penetrating pressure is 500kpa, and it is 0.2 with the mol ratio of NOx to control hexa:1,950 DEG C of maintenance reaction temperature,
Reaction 2s, the product that obtains of reaction is N2, CO, CO2, H2O, with the concentration of NOx before and after detection analysis instrument detection process, is calculated
Going out NOx removal efficiency is86%。
Embodiment 4
800Kg urea is 22Generation ammonia and cyanuric acid are heated under the conditions of 0 DEG C.The ammonia for reacting generation is passed through 1000kg first
The mixing liquid of hexa and ammoniacal liquor is obtained in aldehyde solution.Pending flue gas is sprayed into using the mixing liquid as denitrfying agent
In, penetrating pressure is 500kpa, and it is 0.2 with the mol ratio of NOx to control hexa:1,950 DEG C of maintenance reaction temperature, instead
Answer 2s, the product that reaction is obtained is N2, CO, CO2, H2O, with the concentration of NOx before and after detection analysis instrument detection process, calculate
NOx removal efficiency is 79%.
Embodiment 5
1000kg urea heats generation ammonia and cyanuric acid under the conditions of 260 DEG C.The ammonia for reacting generation is passed through 1000kg
The mixing liquid of hexa and ammoniacal liquor is obtained in formalin.Pending cigarette is sprayed into using the mixing liquid as denitrfying agent
In gas, penetrating pressure is 500kpa, and it is 0.2 with the mol ratio of NOx to control hexa:1,950 DEG C of maintenance reaction temperature,
Reaction 2s, the product that obtains of reaction is N2, CO, CO2, H2O, with the concentration of NOx before and after detection analysis instrument detection process, is calculated
It is 83% to go out NOx removal efficiency.
Embodiment 5
1000kg urea heats generation ammonia and cyanuric acid under the conditions of 200 DEG C.The ammonia for reacting generation is passed through 1000kg
The mixing liquid of hexa and ammoniacal liquor is obtained in formalin.Pending cigarette is sprayed into using the mixing liquid as denitrfying agent
In gas, penetrating pressure is 500kpa, and it is 0.2 with the mol ratio of NOx to control hexa:1,950 DEG C of maintenance reaction temperature,
Reaction 2s, the product that obtains of reaction is N2, CO, CO2, H2O, with the concentration of NOx before and after detection analysis instrument detection process, is calculated
It is 82% to go out NOx removal efficiency.
Claims (8)
1. a kind of denitration method for flue gas of coproduction cyanuric acid, it is characterised in that comprise the following steps：
（1）Urea carries out condensation reaction under the conditions of 200-260 DEG C；Condensation reaction generates cyanuric acid solid；
（2）The ammonia of condensation reaction generation is passed through formalin, is reacted；
（3）Step（2）The reaction mass for obtaining enters as denitrfying agent injection denitration reaction area under 500-1100 DEG C of temperature conditionss
Row denitration；
Urea is 1-1.5 with the mol ratio of formaldehyde in formalin:1.
2. denitration method for flue gas according to claim 1, it is characterised in that the reaction temperature of urea is 220 DEG C.
3. denitration method for flue gas according to claim 1 or claim 2, it is characterised in that urea with formalin formaldehyde mole
Than being 1.08-1.35：1.
4. denitration method for flue gas according to claim 3, it is characterised in that step（3）" the step（2）The reaction for obtaining
Material is used as denitrfying agent injection denitration reaction area " injection pressure be 500-1000kpa.
5. denitration method for flue gas according to claim 4, it is characterised in that the temperature conditionss of step 3 are 900-1100 DEG C.
6. denitration method for flue gas according to claim 5, it is characterised in that the reaction time of step 3 denitration reaction is 1-5s.
7. denitration method for flue gas according to claim 6, it is characterised in that hexa and denitration reaction in denitrfying agent
The mol ratio of the NOx in area is 0.1-0.8：1.
8. denitration method for flue gas according to claim 7, it is characterised in that in hexa and denitration reaction area
The mol ratio of NOx is 0.2-0.5：1.
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| CN201710066660.3A CN106807201A (en) | 2017-02-07 | 2017-02-07 | A kind of denitration method for flue gas of coproduction cyanuric acid |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068888A (en) * | 2010-12-28 | 2011-05-25 | 北京博奇电力科技有限公司 | Method for simultaneously desulfurizing and denitrating flue gas by wet method |
| CN102553412A (en) * | 2012-02-10 | 2012-07-11 | 山东大学 | Method for denitrifying flue gas by using amino reducing agent with high reaction activity |
| CN103769240A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for selective catalytic reduction denitration reactions |
| CN104014232A (en) * | 2014-06-24 | 2014-09-03 | 山东大学 | Method for performing smoke desulfurization and denitrification by using urea co-production preparation technology |
| CN104826669A (en) * | 2015-04-26 | 2015-08-12 | 重庆大学 | Alkali washing liquid for regenerating SCR denitration catalysts and application thereof |
| CN105617818A (en) * | 2015-10-12 | 2016-06-01 | 江苏蓝电环保股份有限公司 | Solvent for recovering SO2 from industrial waste gas |
-
2017
- 2017-02-07 CN CN201710066660.3A patent/CN106807201A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068888A (en) * | 2010-12-28 | 2011-05-25 | 北京博奇电力科技有限公司 | Method for simultaneously desulfurizing and denitrating flue gas by wet method |
| CN102553412A (en) * | 2012-02-10 | 2012-07-11 | 山东大学 | Method for denitrifying flue gas by using amino reducing agent with high reaction activity |
| CN103769240A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for selective catalytic reduction denitration reactions |
| CN104014232A (en) * | 2014-06-24 | 2014-09-03 | 山东大学 | Method for performing smoke desulfurization and denitrification by using urea co-production preparation technology |
| CN104826669A (en) * | 2015-04-26 | 2015-08-12 | 重庆大学 | Alkali washing liquid for regenerating SCR denitration catalysts and application thereof |
| CN105617818A (en) * | 2015-10-12 | 2016-06-01 | 江苏蓝电环保股份有限公司 | Solvent for recovering SO2 from industrial waste gas |
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Application publication date: 20170609 |
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