CN1785522A - Desulfur denitrogen catalyst of fuel coal, fuel oil boiler smoke and its desulfur denitrogen method - Google Patents
Desulfur denitrogen catalyst of fuel coal, fuel oil boiler smoke and its desulfur denitrogen method Download PDFInfo
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- CN1785522A CN1785522A CN 200510126075 CN200510126075A CN1785522A CN 1785522 A CN1785522 A CN 1785522A CN 200510126075 CN200510126075 CN 200510126075 CN 200510126075 A CN200510126075 A CN 200510126075A CN 1785522 A CN1785522 A CN 1785522A
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Abstract
A catalyst for desulfurizing and denitrifying the fume generated by the boiler burning coal or oil is prepared from sodium hydroxide (16-20 Wt%), urea (34-50), ethanolamine (5-8) and biethanolamine (29-45). Its desulfurizing and denitrifying method includes such steps as mixing its raw materials with water, and proportionally spraying the solution into the flue of boiler. Its desulfurizing and denitrifying rates are respectively more than 95% and more than 50%.
Description
Technical field
The invention belongs to the desulfurization removing nitric technical field of fire coal, oil burning boiler flue gas, relate in particular to the catalyst of a kind of chemical method fire coal, oil burning boiler flue gas desulfuration and denitrification, and use this catalyst to carry out the method for flue gas desulfuration and denitrification.
Background technology
Fire coal or oil burning boiler give off a large amount of sulfur dioxide and nitrogen oxide, if utilize traditional calcium injection and desulfurization technology, are difficult to remove.The desulfurizer in present domestic most power plants all spends huge sums from external introduction, and the flue gas desulfuration and denitrification cost is higher.The power plant will consume a large amount of coal and fuel oil every year, and a large amount of sulfur dioxide and the nitrogen oxide that give off simultaneously do great damage to environment, and this pollution problem is the problem that state key is paid close attention to always.
At present, adopting the interior spray of stove calcium carbonate both at home and abroad mostly is the method for limestone powder, and sulfur in smoke is removed.This method needs huge equipment, and invest hugely increases operating cost again, and desulfuration efficiency is low, and key is the nitrogen oxide that can't remove generation, present also do not have small investment, operating cost low, solve the high technology of desulfurization and denitrifying oxide and efficient simultaneously.
Disclosed Chinese patent application 03113768.7 provided a kind of urea seeding agent smoke treatment method of desulfurization removing nitric simultaneously in 2003, this method is made absorbent with urea, flue gas enters continuously from the absorption tower import, with the abundant hybrid reaction of absorption liquid, removes SO in the absorption tower
2And NO
X, it is characterized in that, adopt titanium dioxide or diatomite to make the catalyst preparation absorption liquid, and reclaim sulfuric acid ammonium and ammonium nitrate are made fertilizer.Urea in this method can only be as the agent that removes of inorganic sulfur, can not be converted into inorganic sulfur with the organic sulfur removal in the flue gas or with organic sulfur, simple urea can not effectively reduce the acidity of flue gas, so its desulfurization and denitrification effect are unsatisfactory, and the value of commercial Application is low.
Summary of the invention
The purpose of this invention is to provide a kind of desulfurization removing nitric efficient height, can effectively remove the organic sulfur in the flue gas, consolidate the high fire coal of sulphur residue stability, the catalyst of oil burning boiler flue gas desulfuration and denitrification simultaneously, and use this catalyst to carry out the method for flue gas desulfuration and denitrification.
The technical solution used in the present invention is as follows;
The desulphurization and denitrification catalyst of a kind of fire coal, oil burning boiler flue gas is characterized in that this catalyst is made up of following raw materials by weight percent: NaOH 16～20%, urea 34～50%, monoethanolamine 5～8%, diethanol amine 29～45%.
This catalyst is made up of following raw materials by weight percent: NaOH 19%, urea 42%, monoethanolamine 7%, diethanol amine 32%.
Described NaOH is the technical grade NaOH of purity 97%, described urea is the technical grade urea of total nitrogen content 46%, affiliated monoethanolamine is the technical grade monoethanolamine of total amine amount 99%, and described diethanol amine is the technical grade diethanol amine of total amine amount 96%.
Use above-mentioned catalyst to carry out the desulfurizing and denitrifying method of fire coal, oil burning boiler flue gas, it is characterized in that each raw material components of catalyst joined and mix the solution that obtains catalyst in the water of raw material gross weight 400～500%, in the flue of fire coal or oil burning boiler, spray this catalyst solution, the sprinkling amount is a catalyst solution weight: weight of fuel=6～8: 1, the percentage by weight of described each raw material of catalyst consists of: NaOH 16～20%, urea 34～50%, monoethanolamine 5～8%, diethanol amine 29～45%.
NaOH described in the catalyst raw material is the technical grade NaOH of purity 97%, described urea is the technical grade urea of total nitrogen content 46%, affiliated monoethanolamine is the technical grade monoethanolamine of total amine amount 99%, and described diethanol amine is the technical grade diethanol amine of total amine amount 96%.
Above-mentioned NaOH, urea, monoethanolamine and diethanol amine raw material are the commercial industrial product.There are Chlor-Alkali Plant, Qilu Petro-chemical Co., epoxy resin factory of BaLing Petroleum Chemical Engineering Co., Ltd, Tianjin chemical industry Co., Ltd in the manufacturer of described NaOH; There are Lanzhou chemical fertilizer factory of chemical industrial company, chemical fertilizer factory of Qilu Petrochemical company, Daqing petrochemical chemical fertilizer factory in the manufacturer of described urea; There are chemical industry three factories of Shanghai Gaoqiao petro-chemical corporation, Qing Feng chemical plant, Shenyang in the manufacturer of described monoethanolamine; There are chemical industry three factories of Shanghai Gaoqiao petro-chemical corporation, Shenyang Qing Feng chemical industry two factories in the manufacturer of described diethanol amine.
NaOH in the catalyst can reduce acidity, shortening reaction time, the raising desulfurization removing nitric efficient of flue gas when the catalytic desulfurization denitrification reaction; Urea is that inorganic sulfur is deviate from reactant, can improve the long term storage stability of desulfurized effect in its flue gas and solid sulphur residue sulfate, so that solid sulphur residue can be applied on the construction material.Described monoethanolamine be in the flue gas organic sulfur deviate from agent, can improve desulfurization removing nitric efficient.Described diethanol amine is the reforming catalyst that organic sulfur changes into inorganic sulfur, after it is transformed into inorganic sulfur with the organic sulfur catalysis in the flue gas earlier, the inorganic sulfur that cooperates NaOH, urea, monoethanolamine to have converted to again is cured in the residue, sulphur long-term stability in the residue is not rebounded, can do construction material and use.Each material combination of this catalyst uses fire coal or oil burning boiler fume emission after can guaranteeing to handle to reach national environmental standard.
The preparation method of the desulphurization and denitrification catalyst of this fire coal, oil burning boiler flue gas is fairly simple, and above-mentioned NaOH, urea, monoethanolamine and diethanol amine raw material are mixed by weight ratio and can obtain.Also can be when desulfurization removing nitric raw material directly be added to the water and be mixed with catalyst solution.When this catalyst carries out the desulfurization removing nitric of fire coal, oil burning boiler flue gas, the amount of the catalyst solution that can spray according to the concentration adjustment of sulfur dioxide in flue gas.General sulfur dioxide in flue gas concentration is 1200mg/m
3～8000mg/m
3, desulphurization and denitrification catalyst is separated sulfate in the reacted catalyst solution of desulfurization removing nitric and the solid slag of nitrate by equipment for separating liquid from solid with after flue gas fully contacts, and part has neither part nor lot in the desulfurization removing nitric catalyst for reaction and can continue to recycle.Isolated sulfate and nitrate can be used as building material and use.
Beneficial effect of the present invention is that the desulphurization and denitrification catalyst cost of material of this fire coal, oil burning boiler flue gas is low, and preparation is simple, can carry out the desulfurization removing nitric reaction in same operation simultaneously, and can effectively remove the organic sulfur in the flue gas.It is simple to use this catalyst to carry out the desulfurizing and denitrifying method of fire coal, oil burning boiler flue gas, does not need burner is changed simultaneously, can operate by existing smoke eliminator, and desulfurization degree can reach more than 95%, and denitrification percent reaches more than 50%.The desulphurization and denitrification catalyst of this fire coal, oil burning boiler flue gas and the desulfurizing and denitrifying method that uses this catalyst to carry out fire coal, oil burning boiler flue gas can be used for the gas cleaning of the boilers such as fire coal, residual oil and pitch of various combustion of sulfur, nitrogenate.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment, and the percentage among the following embodiment is weight percent concentration except that specified otherwise.
Embodiment 1 gets raw material by following component and proportioning: 18kg NaOH, 36kg urea, 6kg monoethanolamine, 40kg diethanol amine mix the desulphurization and denitrification catalyst that obtains fire coal, oil burning boiler flue gas.
Embodiment 2 is an experimental facilities with certain power plant coal-burning boiler, is fuel with the Taiyuan fire coal, and this fire coal sulfur content is 2.4%, and sulfur dioxide in flue gas content is 3800mg/Nm
3～4000mg/Nm
3About.Discharging fume increase by one column for smoke purification.The water of the 100kg catalyst of embodiment 1 preparation and 500kg is hybridly prepared into the aqueous solution of catalyst, by the spraying of purifying column top it is fully contacted with flue gas this aqueous solution, the spraying amount is 6: 1 by catalyst solution weight and coal-fired weight ratio, and the agent sulphur ratio of sulphur is 3: 1 in the catalyst of consumption and the coal.Flue gas after desulfurization removing nitric is handled reaches discharge standard fully, and the sulfur-bearing and the nitrogen content correction data of flue gas see Table 1 before and after this processing.
The sulfur-bearing and the nitrogen content correction data of flue gas before and after table 1 embodiment 2 handles
| Project name | Smoke emissioning concentration (mg/Nm before handling 3) | Handle back smoke emissioning concentration (mg/Nm 3) |
| Sulfur dioxide | 3860 | 166 |
| Nitrogen oxide | 846 | 4.8 |
As can be seen from the above table, the flue gas after catalyst that the employing embodiment of the invention provides and desulfurizing and denitrifying method are handled can reach discharge standard, and the desulfurization degree that calculates with sulfur dioxide reaches 95.7%, and denitrification percent reaches 51.8%.
Embodiment 3 gets raw material by following component and proportioning: 20kg NaOH, 34kg urea, 8kg monoethanolamine, 38kg diethanol amine, obtain the desulphurization and denitrification catalyst of fire coal, oil burning boiler flue gas, each raw material of this catalyst is joined in the 400kg water be made into catalyst solution.The technical indicator of this catalyst sees Table 2.
Every technical indicator of the desulphurization and denitrification catalyst solution of table 2 coal and oil boiler smoke
| Project | Index |
| Density, g/cm 3 | 1.27 |
| Kinematic viscosity, mm 2/s(20℃) | 4.00 |
| Color | Water white transparency |
| Mechanical admixture, % | 0.03 |
| Water-soluble soda acid pH value | 14 |
Embodiment 4 gets raw material by following component and proportioning: 16kg NaOH, 50kg urea, 5kg monoethanolamine, 29kg diethanol amine, obtain the desulphurization and denitrification catalyst of fire coal, oil burning boiler flue gas, each raw material of this catalyst is joined in the 500kg water successively be made into catalyst solution.
Embodiment 5 is an experimental facilities with the oil burning boiler, is fuel with the Guangdong high-sulfur residual oil, and the sulfur content of this high-sulfur residual oil is 3.2%, and sulfur dioxide in flue gas content is 6000mg/Nm
3About.Discharging fume increase by one smoke eliminator, pass through in this device of flue gas, the aqueous catalyst solution of embodiment 4 preparations is met the spraying of flow of flue gas direction by the purifier top makes it fully contact with flue gas, the spraying amount is 8: 1 by catalyst solution weight and coal-fired weight ratio, and the agent sulphur ratio of sulphur is 3: 1 in the catalyst of consumption and the residual oil.Flue gas after desulfurization removing nitric is handled reaches discharge standard fully, and the sulfur-bearing and the nitrogen content correction data of flue gas see Table 3 before and after this processing.
The sulfur-bearing and the nitrogen content correction data of flue gas before and after table 3 embodiment 5 handles
| Project name | Smoke emissioning concentration (mg/Nm before handling 3) | Handle back smoke emissioning concentration (mg/Nm 3) |
| Sulfur dioxide | 6100 | 244 |
| Nitrogen oxide | 480 | 184 |
Claims (5)
1. the desulphurization and denitrification catalyst of a fire coal, oil burning boiler flue gas is characterized in that this catalyst is made up of following raw materials by weight percent: NaOH 16～20%, urea 34～50%, monoethanolamine 5～8%, diethanol amine 29～45%.
2. the catalyst of fire coal according to claim 1, oil burning boiler flue gas desulfuration and denitrification is characterized in that this catalyst is made up of following raw materials by weight percent: NaOH 19%, urea 42%, monoethanolamine 7%, diethanol amine 32%.
3. the desulphurization and denitrification catalyst of fire coal according to claim 1, oil burning boiler flue gas, it is characterized in that described NaOH is the technical grade NaOH of purity 97%, described urea is the technical grade urea of total nitrogen content 46%, described monoethanolamine is the technical grade monoethanolamine of total amine amount 99%, and described diethanol amine is the technical grade diethanol amine of total amine amount 96%.
4. the desulfurizing and denitrifying method of the described fire coal of claim 1, oil burning boiler flue gas, it is characterized in that each raw material components of catalyst joined and mix the solution that obtains catalyst in the water of raw material gross weight 400%～500%, in the flue of fire coal or oil burning boiler, spray this catalyst solution, the sprinkling amount is a catalyst solution weight: weight of fuel=6～8: 1, the percentage by weight of described each raw material of catalyst consists of: NaOH 16～20%, urea 34～50%, monoethanolamine 5～8%, diethanol amine 29～45%.
5. the desulfurizing and denitrifying method of fire coal according to claim 4, oil burning boiler flue gas, it is characterized in that the NaOH described in the catalyst raw material is the technical grade NaOH of purity 97%, described urea is the technical grade urea of total nitrogen content 46%, affiliated monoethanolamine is the technical grade monoethanolamine of total amine amount 99%, and described diethanol amine is the technical grade diethanol amine of total amine amount 96%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218264A (en) * | 2011-06-27 | 2011-10-19 | 叶汉华 | Coal-fired power plant flue gas sulfur dioxide catalytic desulfurization production and technical flow |
| CN101560425B (en) * | 2009-06-04 | 2012-09-05 | 北京弘扬紫东环保科技有限公司 | Novel coal sulphur-fixing agent, preparation method and application thereof |
| CN111085229A (en) * | 2018-10-23 | 2020-05-01 | 南京化学工业园环保产业协同创新有限公司 | Cocatalyst for reducing and denitrifying ammonia gas in coal-fired flue gas |
| CN115193239A (en) * | 2022-07-04 | 2022-10-18 | 江西雄瓷科技有限公司 | Preparation method of composite liquid desulfurizer |
Family Cites Families (8)
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|---|---|---|---|---|
| US4180548A (en) * | 1978-12-22 | 1979-12-25 | Exxon Research & Engineering Co. | Process for selective removal of cyclic urea from hindered amine gas treating solution |
| US5705141A (en) * | 1990-11-21 | 1998-01-06 | Lhoist Researche Et Developpement S.A. | Calcium and/or magnesium hydroxide, and preparation and use thereof |
| CN1091636C (en) * | 1994-06-30 | 2002-10-02 | 纳可环技公司 | Multi-step process for reucing no and so |
| US6165432A (en) * | 1998-09-30 | 2000-12-26 | The Dow Chemical Company | Composition and process for removal of acid gases |
| CN1085103C (en) * | 1998-11-13 | 2002-05-22 | 中国石油化工集团公司 | Desulfurizer for refining gas and its preparation method |
| US6722295B2 (en) * | 2000-09-29 | 2004-04-20 | Bert Zauderer | Method for the combined reduction of nitrogen oxide and sulfur dioxide concentrations in the furnace region of boilers |
| CN1120033C (en) * | 2001-04-18 | 2003-09-03 | 武汉大学 | Method for removing sulfur dioxide from flue gas |
| CN1139422C (en) * | 2001-12-30 | 2004-02-25 | 国家环境保护总局华南环境科学研究所 | Wet urea additive process for simultanously desulfurizing and denitrification |
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2005
- 2005-11-30 CN CNB2005101260755A patent/CN100344378C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560425B (en) * | 2009-06-04 | 2012-09-05 | 北京弘扬紫东环保科技有限公司 | Novel coal sulphur-fixing agent, preparation method and application thereof |
| CN102218264A (en) * | 2011-06-27 | 2011-10-19 | 叶汉华 | Coal-fired power plant flue gas sulfur dioxide catalytic desulfurization production and technical flow |
| CN102218264B (en) * | 2011-06-27 | 2014-09-03 | 叶汉华 | Coal-fired power plant flue gas sulfur dioxide catalytic desulfurization production and technical flow |
| CN111085229A (en) * | 2018-10-23 | 2020-05-01 | 南京化学工业园环保产业协同创新有限公司 | Cocatalyst for reducing and denitrifying ammonia gas in coal-fired flue gas |
| CN115193239A (en) * | 2022-07-04 | 2022-10-18 | 江西雄瓷科技有限公司 | Preparation method of composite liquid desulfurizer |
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