CN1139422C - Wet urea additive process for simultanously desulfurizing and denitrification - Google Patents
Wet urea additive process for simultanously desulfurizing and denitrification Download PDFInfo
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- CN1139422C CN1139422C CNB011301546A CN01130154A CN1139422C CN 1139422 C CN1139422 C CN 1139422C CN B011301546 A CNB011301546 A CN B011301546A CN 01130154 A CN01130154 A CN 01130154A CN 1139422 C CN1139422 C CN 1139422C
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- urea
- absorption tower
- absorption
- pump
- flue gas
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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
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Abstract
The present invention relates to a wet urea additive method for simultaneous desulphurization and denitrification by flue gas, which belongs to a purifying and treating technology of the flue gas. The equipment of the present invention is composed of a dispensing tank with a stirrer, a dosing pump, an absorption tower, a circulating pump, a storing pool for concentrated circulating and absorbing liquid, an evaporating feed pump, an evaporator, a drying feed pump and a dryer which are mutually connected through pipelines. The method for simultaneous desulphurization and denitrification is characterized in that urea is used as an absorbing agent, and organic amines or phosphates of certain amount are additionally added to be used as additives; the flue gas continuously passes through the absorption tower and is fully mixed with absorption liquid to react; thus, the SO2 removing rate reaches more than 95%, and the NO<x> removing rate reaches more than 80%; ammonium sulfate is recovered to be used as fertilizer, wherein the absorption liquid is formed by that the additives of the organic amines, such as ethanediamine, triethanolamine, etc., are added into the urea or the additives of the phosphates, such as ammonium phosphate (sodium), diammonium phosphate (sodium), etc., are added into the urea to prepare the absorption liquid in the dispensing tank; the absorption tower is an atomizing absorption tower without a nozzle, and the flue gas and the urea react in the absorption tower to generate ammonium sulfate and nitrogen; the ammonium sulfate is used as the fertilizer, and the nitrogen is discharged harmlessly. The present invention has the advantages that SO2 and NO<x> can be stably removed at high efficiency, the SO2 removing rate reaches more than 95%, and the NO<x> removing rate reaches more than 80%; the present invention also has the advantages of no secondary pollution, less investment and low operating cost.
Description
(1) technical field:
The present invention is a wet urea additive process for simultanously desulfurizing and denitrification, belongs to the waste gas pollution control and treatment in the environmental pollution prevention and control, and particularly boiler flue gas purification is administered technology.
(2) background technology:
Now, the environment acidifying has become one of key factor of restriction socio-economic development, and the environment acidifying mainly comes from the sulfur dioxide SO with toxic emission
2With oxynitrides NO
xProcesses such as industrial production, communications and transportation, castoff burning and civilian burning all can give off SO
2, NO
x, particularly the boiler combustion pollution is the most serious, 90% SO in the air
2With 60% NO
xFrom the boiler combustion discharged flue gas.China SO
2And NO
xAnnual emissions nineteen ninety-five just ranks first in the world, is respectively 2,370 ten thousand tons and 7,700,000 tons, and day by day serious, has accounted for 30% of area to acid rain district in 2000.Domestic tens thousand of the boilers of China have the directly discharging without any processing of 90% above flue gas, a large amount of SO
2And NO
xEnter environment, must tighten control as early as possible and administer.At present, both at home and abroad the method for simultanously desulfurizing and denitrification mainly contains following several: (1) plasma method, it comprises two kinds of electron beam and impulse electric coronas, is to utilize high energy electron to make water H in the flue gas
2O, oxygen O
2Equimolecular is activated, ionization or cracking, produces strong oxidizing property active particles such as a large amount of electronics and free radical, makes SO
2And NO
xOxidized, under the situation of injecting adsorbent ammonia, generate ammonium sulfate and ammonium nitrate fertilizer, day should technology industrial applications; Korea S has the people to utilize low-temperature plasma reactor to carry out flue gas desulfuration and denitrification, a kind of desulfurization from flue gas that condenser promotes low-temperature plasma reaction, the method for denitrogenation promptly are set in low-temperature plasma reactor, and this technology produces secondary wastewater and pollutes and be difficult to handle.Plasma method technology is all very complicated, adopts ammonia to make the volatile ammonia that causes of absorbent and loses and exhaust pollution; (2) catalysis method is a desulfurization removing nitric technology under the catalyst action condition.Desulfurization removing nitric technology: SO in the time of, the recyclable utilization of sulphur resource renewable as: a kind of dry type, desulfurizing agent
2And NO
xContain sodium carbonate Na at high-ratio surface
2CO
3Plumbous matter absorbent on the catalysis absorption technique; Similarly passed through the catalysis technique after the dedusting in addition earlier, as: behind the bag-type dust, flue gas is while desulfurization removing nitric technology under ammonia and catalyst synergy, be in lab scale or pilot scale stage at present, the direct acting factor of catalysis method is that Preparation of catalysts and regeneration are complicated, adopts ammonia to make the volatile ammonia that causes of absorbent simultaneously and loses and exhaust pollution; (3) wet chemical domesticly utilizes the soda compound solution that industrial smoke is carried out comprehensive purifying to handle, and this method is the same with low-temperature plasma technology to be produced secondary wastewater and pollute and be difficult to processing.Chemical method is used for the desulfuration in furnace denitrogenation mostly.Urea is made the absorbent wet method and is removed SO in the flue gas simultaneously
2And NO
xResearch do not appear in the newspapers at home, only have Russian Mendeleev chemical engineering institute to study abroad, see also " chemical science and technology is dynamic ", 1994.NO4, P41～43, (Xu Weizheng translates---with the new technology of urea purifying flue gas), but stable extreme difference is difficult to repeat implement.Urea and additive associating wet flue gas desulfurization removing nitric simultaneously do not appear in the newspapers, and its additive is got side reaction, stable absorption and the effect of raising purification efficiency of suppressing.
(3) summary of the invention:
Purpose of the present invention is exactly to pollute and be difficult to processing or Preparation of catalysts and regeneration technology complexity, adopt ammonia to do that absorbent is volatile to be caused ammonia loss and exhaust pollution and urea to make the absorbent wet method to remove SO in the flue gas simultaneously in order to overcome and to solve the secondary wastewater that has complex process, generation in the technology of existing desulfurization removing nitric
2And NO
xThe method poor stability, the shortcoming and the problem that are difficult to repeat to implement etc., the research invention is a kind of to be absorbent with urea, adds a certain amount of additive, makes the SO in the flue gas
2, NO
xThe wet urea additive flue gas simultaneous desulfurization that removes to reach the purification treatment purpose takes off the helium method stability and high efficiency simultaneously.
The present invention realizes by following technical proposals: the wet urea additive equipment of desulfurizing and denitrifying method simultaneously constitutes structural representation as shown in Figure 1; Its technological process block-diagram as shown in Figure 2.It is connected and composed jointly by dispensing canister 1, mixer 2, dosing pump 3, absorption tower 4, circulating pump 5, dense circulating absorption solution storage pond 6, evaporation feed pump 7, evaporimeter 8, dry feed pump 9, drying machine 10, and its mutual alignment and annexation are: absorption tower 4 has the dispensing canister 1 of mixer 2, dense circulating absorption solution storage pond 6 to be connected with interior device respectively by pipeline and dosing pump 3, pipeline and circulating pump 5 respectively; Evaporimeter 8 is connected with dense circulating absorption solution storage pond 6, drying machine 10 respectively by pipeline and evaporation feed pump 7, pipeline and dry feed pump 9 respectively.
Wet urea additive process for simultanously desulfurizing and denitrification is as follows: make absorbent with urea, add a certain amount of organic amine or phosphoric acid salt and make additive, flue gas enters from absorption tower import B, passes through the absorption tower continuously, in the absorption tower,, make SO in its flue gas with the abundant hybrid reaction of absorption liquid
2Clearance reaches more than 95%, NO
xClearance reaches more than 80%, and reclaim sulfuric acid ammonium comprehensive utilization is as fertilizer; Its technical process is: (1) urea absorbent adds the absorption liquid that organic amine additive or urea absorbent add the phosphoric acid salt additive and is formulated as: in 1.2 meters * 1.5 meters Agitation Tanks 1 of of band mixer 2, add entry, urea and organic amine additive---ethylenediamine or triethanolamine or urea and phosphoric acid salt additive---ammonium phosphate (or sodium) or diammonium hydrogen phosphate (or sodium), making content of urea is 5～30%, and the content of organic amine additive-ethylenediamine or triethanolamine or phosphoric acid salt additive-ammonium phosphate (or sodium) or diammonium hydrogen phosphate (or sodium) is (50～500) * 10
-4%, the content of water are 69.95～94.995%, make absorption liquid after stirring with 12 rev/mins mixing speed with mixer 2; (2) with dosing pump 3 absorption liquid being pumped into effective depth is 1.0～3.0 meters, in the no nozzle atomization absorption tower 4 that diameter is 0.6 meter, and with circulating pump 5 forced circulation, flue gas is continuously by absorption tower 4, and in absorption tower 4, generating ammonium sulfate and nitrogen with urea reaction, harmless nitrogen and flue gas after being purified are from absorbing cat head A outlet discharging; (3) dense circulating absorption solution enters dense circulating absorption solution pond 6 and stores, after feed pump 7 pumps into evaporimeter 8 evaporation and concentration to 70～85% with dense circulating absorption solution by evaporation again, pump in the drying machine 10 drying by dry feed pump 9 again and make chemical fertilizer ammonium sulfate and emit from outlet C and make comprehensive utilization of resources; Its process conditions are: flue-gas temperature is 40 ℃～250 ℃, SO
2Concentration be (500～4000) * 10
-4%, NO
xConcentration be (300～3000) * 10
-4%, liquid-gas ratio are 0.5～10 liter/cubic metre, and gas speed is 1～5 meter per second; Measure SO in the absorption tower turnover flue gas
2And NO
xConcentration, calculate SO
2And NO
xClearance, SO
2Clearance be more than 95%, NO
xClearance be more than 80%.
The present invention compares with existing process for simultanously desulfurizing and denitrification, has following advantage and beneficial effect.(1) can remove SO simultaneously stably, efficiently
2, NO
x, miniature boiler is smoke abatement simultaneously; (2) byproduct is ammonium sulfate (NH
4)
2SO
4, comprehensive utilization is as fertilizer; And urea absorbent and ammonia absorbent are more not volatile overflows non-secondary pollution with flue gas; (3) near absorption liquid (PH is 5.5～5.8) neutral, and additive has antiseptic effect, and the cost of equipment is low; (4) absorbent urea and byproduct (NH
4)
2SO
4Easily transport, store; (5) absorbent urea has carbonyl C=0, is expected organic sulfide removal combustion product thiophene phenol (a kind of material that industrial catalyst is poisoned) simultaneously, is suitable for the purified treatment of catalysis industrial gas, and range of application is wide; (6) no nozzle high-efficient atomizing absorption tower and traditional spray tower and packed tower relatively can be anti-wear, stop up, be not afraid of flue dust; The absorption efficiency height, the tower body volume is little, and investment and running take province; (7) simple, the small investment of technological process (for wet desulphurization equipment commonly used 1/3～1/2), operating cost has competitiveness; (8) Application and Development of the present invention is polluted and acidification controling environment, and ensures that human social is significant.
(4) description of drawings:
Below Figure of description is further specified as follows: Fig. 1 is the equipment formation structural representation of field trial with wet urea additive while desulfurizing and denitrifying method; Fig. 2 is the technological process block-diagram of the inventive method.Among Fig. 1: the 1st, dispensing canister, the 2nd, mixer, the 3rd, dosing pump, the 4th, absorption tower, the 5th, circulating pump, the 6th, dense circulating absorption solution storage pond: the 7th, evaporation feed pump, the 8th, evaporimeter, the 9th, dry feed pump, the 10th, drying machine; A is a purified gas floss hole pipeline, and B is the gas approach pipeline, and C is an ammonium sulfate outlet pipeline.
(5) specific embodiment:
The inventor thinks and realizes that optimal way of the present invention can be as follows: (1) by shown in Figure 1, design, processing and manufacturing or choose each parts, and for example: dispensing canister 1 can adopt machine-tooled method processing with steel plate; Mixer 2 can be selected the BLD1.5-2-112 type for use; Dosing pump 3 optional Shanghai Shen Yang Bengchang produce WBR-5/7 type dosing pump; Absorption tower 4 optional no nozzle atomization absorption tower TLD types, effective depth can be 1.0～3.0 meters, and diameter can be 0.6 meter; First water pump works, circulating pump 5 optional Guangzhou produces KF50-23 type circulating pump; Evaporimeter 8 optional Huanan Inst. of Environmental Sciences improve the HN-01 type of development and force the outer circulation four-effect evaporator; Drying machine 10 optional Huanan Inst. of Environmental Sciences improve the HN type double hose atomizing dryer of development; The optional Germany of flue gas analyzer produces the portable flue gas analyzer of test360 type; Evaporation feed pump 7 optional TKG2 * 1/2 type, flow is 5m
3/ h, lift are 30 meters the pump of uncapping; Dry feed pump 9 optional TKG2 * 1/2 type, flow is 2m
3/ h, lift are 30 meters the pump of uncapping; Dense circulating absorption solution storage pond 6 can be built into reinforced concrete; (2) choose, behind good each parts of processing and manufacturing, device, can connection be installed by Fig. 1, the described interconnected relationship of shown in Figure 2 and top specification, just can implement experimental rig equipment of the present invention preferably, adopt additive wet method desulfurization removing nitric simultaneously by described technological process of the inventive method and process conditions then, just can reach the object of the invention preferably.The inventor has a lot of successful embodiment through research, the test of long period.Below 4 embodiment are shown in table 1.Table 1:
Claims (2)
1, a kind of equipment of wet urea additive simultanously desulfurizing and denitrification, it is characterized in that: it is by dispensing canister (1), mixer (2), dosing pump (3), absorption tower (4), circulating pump (5), the dense absorption liquid storage pond (6) of following, evaporation feed pump (7), evaporimeter (8), dry feed pump (9), drying machine (10) connects and composes jointly, and its mutual alignment and annexation are: absorption tower (4) are respectively by pipeline and dosing pump (3), pipeline and circulating pump (5) have the dispensing canister (1) of mixer (2) respectively with interior device, dense circulating absorption solution storage pond (6) is connected; Evaporimeter (8) is connected with dense circulating absorption solution storage pond (6), drying machine (10) respectively by pipeline and evaporation feed pump (7), pipeline and dry feed pump (9) respectively.
2, a kind of wet urea additive process for simultanously desulfurizing and denitrification, it is characterized in that: make absorbent with urea, add a certain amount of organic amine or phosphoric acid salt and make additive, flue gas enters from absorption tower import B, pass through the absorption tower continuously, in the absorption tower,, make SO in its flue gas with the abundant hybrid reaction of absorption liquid
2Clearance reaches more than 95%, NO
xClearance reaches more than 80%, and reclaim sulfuric acid ammonium comprehensive utilization is as fertilizer; Its technical process is: (1) urea absorbent adds the absorption liquid that organic amine additive or urea absorbent add the phosphoric acid salt additive and is formulated as: in 1.2 meters * 1.5 meters Agitation Tanks of (1) of band mixer (2), add entry, urea and organic amine additive---ethylenediamine or triethanolamine or urea and phosphoric acid salt additive---ammonium phosphate or sodium phosphate, or diammonium hydrogen phosphate or sodium hydrogen phosphate, making content of urea is 5～30%, the organic amine additive---ethylenediamine or triethanolamine or phosphoric acid salt additive---ammonium phosphate or sodium phosphate, the content of diammonium hydrogen phosphate or sodium hydrogen phosphate is (50～500) * 10
-4%, the content of water are 69.95～94.995%, make absorption liquid after stirring with 12 rev/mins mixing speed with mixer (2); (2) with dosing pump (3) absorption liquid being pumped into effective depth is 1.0～3.0 meters, in the no nozzle atomization absorption tower (4) that diameter is 0.6 meter, and with circulating pump (5) forced circulation, flue gas is continuously by absorption tower (4), and in absorption tower (4), generating ammonium sulfate and nitrogen with urea reaction, harmless nitrogen and flue gas after being purified are from absorbing cat head A outlet discharging; (3) dense circulating absorption solution enters dense circulating absorption solution pond (6) and stores, after (7) pump into evaporimeter (8) evaporation and concentration to 70～85% with dense circulating absorption solution by the evaporation feed pump again, pump in the drying machine (10) drying by dry feed pump (9) again and make chemical fertilizer ammonium sulfate and emit from outlet C and make comprehensive utilization of resources; Its process conditions are: flue-gas temperature is 40 ℃～250 ℃, SO
2Concentration be (500～4000) * 10
-4%, NO
xConcentration be (300～3000) * 10
-4%, liquid-gas ratio are 0.5～10 liter/cubic metre, and gas speed is 1～5 meter per second; Measure SO in the absorption tower turnover flue gas
2And NO
xConcentration, calculate SO
2And NO
xClearance, SO
2Clearance be more than 95%, NO
xClearance be more than 80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011301546A CN1139422C (en) | 2001-12-30 | 2001-12-30 | Wet urea additive process for simultanously desulfurizing and denitrification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011301546A CN1139422C (en) | 2001-12-30 | 2001-12-30 | Wet urea additive process for simultanously desulfurizing and denitrification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1377722A CN1377722A (en) | 2002-11-06 |
| CN1139422C true CN1139422C (en) | 2004-02-25 |
Family
ID=4669779
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011301546A Expired - Fee Related CN1139422C (en) | 2001-12-30 | 2001-12-30 | Wet urea additive process for simultanously desulfurizing and denitrification |
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|---|---|
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| CN1331567C (en) * | 2003-03-18 | 2007-08-15 | 于文波 | Sulfur dioxide removing agent |
| CN100340325C (en) * | 2005-09-29 | 2007-10-03 | 华南理工大学 | Flue gas simultaneous desulfurization and denitrogenation by utilizing triethylenediamine cobalt (III) and carbamide |
| CN100344378C (en) * | 2005-11-30 | 2007-10-24 | 曹志德 | Desulfur denitrogen catalyst of fuel coal, fuel oil boiler smoke and its desulfur denitrogen method |
| CN101653695B (en) * | 2009-09-18 | 2011-06-08 | 王子国 | Method of byproduct compound fertilizer by desulfurizing and denitrifying smoke gas by urea catalytic partial reaction |
| CN103721550B (en) * | 2014-01-23 | 2016-08-17 | 环境保护部华南环境科学研究所 | Flue gas and desulfurizing and denitrifying takes off VOCs absorbent and preparation thereof and application |
| CN103949154B (en) * | 2014-05-08 | 2015-09-23 | 河南铭源环保科技有限公司 | Motor vehicle exhaust emission purified treatment liquid |
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| CN107138044B (en) * | 2017-06-02 | 2020-06-23 | 许昌学院 | Diesel vehicle urea solution with low-temperature performance and preparation method thereof |
| EP3842125A1 (en) | 2017-06-14 | 2021-06-30 | Jiangnan Environmental Protection Group Inc. | Automatic ammonia-adding system and method for ammonia-based desulfurization device |
| CN108722163B (en) | 2017-09-07 | 2019-06-07 | 江苏新世纪江南环保股份有限公司 | A kind of method that ammonia process of desulfurization control absorption process aerosol generates |
| EP3549661A1 (en) * | 2018-04-06 | 2019-10-09 | Yara International ASA | Nox removal from gaseous effluents |
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| CN110732227B (en) | 2018-07-20 | 2023-02-21 | 江南环保集团股份有限公司 | Method and device for treating acid gas |
| CN109173642B (en) * | 2018-10-31 | 2023-09-22 | 华能国际电力股份有限公司 | Treatment system and method for absorption liquid containing nitrite and nitrate after wet flue gas denitration |
| CN110624380B (en) * | 2019-09-30 | 2022-02-18 | 江苏海默环保科技有限公司 | Synergistic desulfurization and denitrification agent and preparation and application thereof |
| CN111957183A (en) | 2019-12-26 | 2020-11-20 | 江苏新世纪江南环保股份有限公司 | Improved ammonia desulphurization method for controlling aerosol generation in absorption process |
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- 2001-12-30 CN CNB011301546A patent/CN1139422C/en not_active Expired - Fee Related
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