CN103585869A - Flue gas purifying method with recyclable alkali absorption liquid - Google Patents

Flue gas purifying method with recyclable alkali absorption liquid Download PDF

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Publication number
CN103585869A
CN103585869A CN201310297877.7A CN201310297877A CN103585869A CN 103585869 A CN103585869 A CN 103585869A CN 201310297877 A CN201310297877 A CN 201310297877A CN 103585869 A CN103585869 A CN 103585869A
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flue gas
sodium
liquid
absorption
alkali
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蒋克旭
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蒋克旭
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses a flue gas purifying method with recyclable alkali absorption liquid, which comprises the following steps of adding atomized ozone into flue gas, and converting nitrogen oxide (NOX) in the flue gas into soluble nitrogen dioxide (NO2); removing SO2, NOX and mercury in the flue gas by adopting alkali liquid as absorption liquid in an absorption tower to obtain absorption liquid; performing solid-liquid separation on the absorption liquid to obtain a mercury-containing precipitate; performing air oxidation and solid-liquid separation on the filtrate to obtain sodium sulfate and sodium nitrate; preparing alkali liquid by taking sodium sulfate as a sodium element; returning the alkali liquid as absorption liquid to a flue gas absorption system for recycling. Since the method realizes recycling of the alkali liquid at the time of desulfurization, denitrification and mercury removal, the problems of high cost by using a great quantity of alkali liquid in current flue gas purification and secondary pollution caused by waste liquid discharge are solved. The method disclosed by the invention has the advantages of simple process, small investment, low operation cost and high pollutant removal rate, the SO2 removal rate exceeds 95%, the NOX removal rate exceeds 80%, and the waste is fully used.

Description

The flue gas purifying method of alkali absorption liquid reusable edible
One, technical field
The present invention relates to and belongs to air pollution control technique and utilization of resources field, specifically makes the flue gas purifying method of alkali absorption liquid reusable edible during a kind of pollutant in removing flue gas.
Two, background technology
Current, maximum in the world population is just being carried with the ecological environment of most fragile in history in China, is carrying the most unprecedented in history resource consumption and economic activity, is faced with in history the most outstanding ecological environment challenge.Contradiction between population and resource, economic development and ecological environment has become the maximum restraining factors of China's Modernization development.Keep sustainable development, just must reduce the pollution of environment Implementing Circular Economy.The energy resource structure of China present stage determined within quite long from now on period, and the coal of still take is main energy supply and consume general layout and can not change.During coal combustion, in flue gas, produce particle, sulfur dioxide (SO 2), oxynitrides (NO x) and the pollutant such as mercury, the pollutant of controlling and removing in coal-fired flue-gas discharge makes it rationally to utilize the effective way that becomes environment protection.
Refuse is the resource mislaying.Flue gas is carried out to desulphurization and denitration and demercuration, not only can improve air quality, but also can carry out recycling to the accessory substance producing after desulphurization and denitration and demercuration, economize on resources, reduce the cost of related industry, improve ecological efficiency, reduce environmental risk.Therefore, carry out the research of air pollution control technique and the utilization of resources, improve and administer the atmospheric environment of China, recycle discarded regenerated resources, to promoting China's sustainable economic development, protecting people's health Jiankang significant.
For reducing pollutant emission in flue gas, the current major part of China's coal-burning boiler has been installed desulfurizer, is mainly Wet Flue Gas Desulfurization Technique.Utilized sulfur dioxide to react and remove sulfur dioxide with the acid-base neutralization of alkaline desulfurizing agent; In flue gas, the harmful substance of oxynitrides exists mainly with the form of NO, according to the easy oxidized character of NO, as long as NO is oxidized to NO 2, can in wet desulphurization device, realize SO 2and NO 2in time, removes.Meanwhile, the mercury compound in snperoxiaized flue gas is soluble in water, with alkali lye, as absorbent, can remove the mercury of 70-80%.But with alkali lye, as absorbent, flue gas is carried out to desulphurization and denitration and demercuration, application alkali lye cost is high, has limited its application.Therefore, realize recycling of alkali lye, low-cost, the high efficiency technology of desulfurization denitration demercuration simultaneously of research and development just seems particularly important.
Three, summary of the invention
In order to solve the deficiencies in the prior art, while the object of this invention is to provide a kind of pollutant in removing flue gas, make the flue gas purifying method of alkali absorption liquid reusable edible.Application the method technique is simple, small investment, and operating cost is low, and pollutants removal rate is high.
The technical scheme that realizes object employing of the present invention is: the flue gas purifying method step of described alkali absorption liquid reusable edible is:
(1) through adding the ozone of atomization in the flue gas of dedusting, insoluble nitrogen oxide (NO x) be converted into soluble nitrogen dioxide (NO 2).
(2) flue gas enters in absorption tower with the pollutant in alkali liquor absorption flue gas, the sedimentary absorption liquid that obtains sodium sulfite, sodium sulphate and sodium nitrate solution and contain heavy metal Hg; Filter absorption liquid, the sediment that contains heavy metal Hg obtaining send non-ferrous metals smelting works' comprehensive utilization, extracts valuable metal mercury, and filtrate is sodium sulfite, sodium sulphate and sodium nitrate; Filtrate, through oxidizing tower air oxidation, is oxidized to sodium sulphate by sodium sulfite, obtains sodium sulphate and sodium nitrate solution, the cooling sodium sulphate of separating out; Sodium sulphate send alkaline system to produce alkali lye; Sodium nitrate solution, through evaporation, crystallization, obtains sodium nitrate product and sells outward.
(3) utilize the product sodium sulphate in flue gas to make alkali lye (NaOH) technique: by the bisphenol-A (industrial goods) of the sodium sulphate of 10~20 parts (weight), 20~40 parts (weight), 10~20 parts of (weight) quick limes and 40~150 parts of (weight) water, put into conversion reaction still and carry out conversion reaction, under agitation be warmed up to 40~90 ℃, react 60~180 minutes.
Conversion reaction formula is: Na 2sO 4+ Ca (OH) 2+ H 2a=CaSO 4+ Na 2a+2H 2o
Reacted reacting liquid filtering, then use 20~50 ℃ of water washing calcium sulfate precipitations, obtain bisphenol-A sodium-salt aqueous solution.
(4) at 30~80 ℃, bisphenol-A sodium-salt aqueous solution is inputted in tower from carbonization tower top, then passes into the flue gas that contains carbon dioxide purification at the bottom of tower, and in tower, the pH of solution is 8~10, and relative density is 1.11~1.3, and cessation reaction, obtains carbodiimide solution; Carbodiimide solution is filtered, and the bisphenol-A obtaining reclaims and returns to conversion procedure, obtains the Na of concentration 10%~15% 2cO 3solution.
Carburizing reagent formula is: Na 2a+CO 2+ H 2o=Na 2cO 3+ H 2a
(5) carry out causticizing reaction: quick lime is put into ashing pond, add water-solubleization, obtain 95% calcium hydroxide, more further remove tiny sand grains through spinning liquid desander; By 10%~15% Na 2cO 3solution, by 0.10~0.20 kilogram of every cubic metre of adding calcium hydroxide, after preparing, put into together causticizing reaction still, and constantly stir, be warming up to 80~96 ℃, react 90 minutes, when solution concentration is 10% left and right (relative density approximately 1.09~1.1), stop reaction, filtration obtains precipitation of calcium carbonate and alkali lye (NaOH) through washing, and alkali lye (NaOH) is got back to the utilization of smoke absorption systemic circulation as absorption liquid, and precipitation of calcium carbonate recoverable is produced quick lime or as building materials.
Causticizing reaction formula is: Na 2cO 3+ Ca (OH) 2=2NaOH+CaCO 3
The invention has the beneficial effects as follows: because the present invention adopts a kind of wet absorption technique, can be to flue gas and desulfurizing and denitrifying demercuration, and can utilize the product in flue gas to make alkali lye (NaOH), realize recycling of alkali absorption liquid, overcome prior art simultaneously and when gas cleaning, used a large amount of alkali absorption liquid costs high, and the discharging of waste liquid producing causes the deficiency of secondary pollution.Technique of the present invention is simple, small investment, and operating cost is low, and pollutants removal rate is high, to SO 2clearance reach more than 95%, to NO xclearance reach more than 80%, the clearance of heavy metal Hg reaches more than 75%, and refuse is fully used.
Four, the specific embodiment
The concrete implementation step of flue gas purifying method of alkali absorption liquid reusable edible of the present invention is:
(1) at 45-200 ℃, by add the ozone of atomization to flue gas in flue, the insoluble nitrogen oxide (NO in flue gas x) be converted into can be easily molten nitrogen dioxide (NO 2).Ozone and NO xmol ratio be 0.5~2.5: 1.Reaction time 1~10 second.
(2) flue gas enters in absorption tower with the pollutant in alkali liquor absorption flue gas, the sedimentary absorption liquid that obtains sodium sulfite, sodium sulphate and sodium nitrate solution and contain heavy metal Hg; Absorption tower temperature is 45 ℃~95 ℃, and alkali liquor absorption agent is 0.25~1: 1000 with flue gas volume ratio.Filter absorption liquid, the sediment that contains heavy metal Hg obtaining send non-ferrous metals smelting works' comprehensive utilization, extracts valuable metal mercury, and filtrate is sodium sulfite, sodium sulphate and sodium nitrate; Filtrate, through oxidizing tower air oxidation, is oxidized to sodium sulphate by sodium sulfite, obtains sodium sulphate and sodium nitrate solution, the cooling sodium sulphate of separating out; Sodium sulphate send alkaline system to produce alkali lye; Sodium nitrate solution, through evaporation, crystallization, obtains sodium nitrate product and sells outward.
(3) utilize product making alkali lye (NaOH) technique in flue gas to be: by the bisphenol-A (industrial goods) of the sodium sulphate of 10~20 parts (weight), 20~40 parts (weight), 10~20 parts of (weight) quick limes and 40~150 parts of (weight) water, put into conversion reaction still and carry out conversion reaction, under agitation be warmed up to 40~90 ℃, react 60~180 minutes.
Conversion reaction formula is: Na 2sO 4+ Ca (OH) 2+ H 2a=CaSO 4+ Na 2a+2H 2o, by reacted reacting liquid filtering, with 20~50 ℃ of water washing calcium sulfate precipitations, obtains the aqueous solution of bisphenol-A sodium salt.
(4) at 30~80 ℃, the aqueous solution of bisphenol-A sodium salt is inputted in tower from carbonization tower top, then passes into the flue gas that contains carbon dioxide purification at the bottom of tower, and in tower, the pH of solution is 8~10, and relative density is 1.1~1.3, cessation reaction.Carbodiimide solution is filtered, and the recovery bisphenol-A obtaining, returns to conversion procedure, obtains concentration and be 10%~15% Na 2cO 3solution.
Carburizing reagent formula is: Na 2a+CO 2+ H 2o=Na 2cO 3+ H 2a
(5) carry out causticizing reaction: quick lime is put into ashing pond, add water digestion, obtain 95% calcium hydroxide, more further remove tiny sand grains through spinning liquid desander; By 10%~15% Na 2cO 3solution, by 0.10~0.20 kilogram of every cubic metre of adding calcium hydroxide, after preparing, put into together causticizing reaction still, and constantly stir, be warming up to 80-96 ℃, react 90 minutes, when alkali lye (NaOH) concentration is 10% left and right (relative density approximately 1.09~1.1), stop reaction, filtration obtains precipitation of calcium carbonate and alkali lye (NaOH) through washing, and alkali lye (NaOH) is got back to the utilization of smoke absorption systemic circulation as absorption liquid, and precipitation of calcium carbonate recoverable is produced quick lime or as building materials.
Causticizing reaction formula is: Na 2cO 3+ Ca (OH) 2=2NaOH+CaCO 3
Described bisphenol-A is the present invention's acidulous material used, and its acidity, between water and carbonic acid, and is a kind of water-fast solid.Above-mentioned acidulous material is except bisphenol-A, and spendable acidulous material also has derivative (being ethylphenol, cresols, chlorophenic acid, chlorophenesic acid, trichlorophenol, 2,4,6,-T, monobromophenol, dibromophenol, tribromphenol), thiophenol, mercaptan, naphthols, silicic acid, boric acid, aluminium hydroxide and the zinc hydroxide etc. of phenol and phenol.
Described alkali lye is sodium carbonate, sodium acid carbonate/NaOH.
Described ozone is from ozone generator, and raw materials used is air or oxygen, preferably air.
Described absorption tower can adopt any one in spray column, packed tower, liquid column tower, plate column and valve tower.
Described conversion reaction still is enamel or the stainless steel cauldron of jacketed and agitator.
Described carbonators is any one in packed tower, plate column and valve tower.
Described causticizing reaction still is enamel or the stainless steel cauldron of jacketed and agitator.

Claims (1)

1. a flue gas purifying method for alkali absorption liquid reusable edible, the method is:
First by adding the ozone of atomization in the process flue gas of dedusting, insoluble nitrogen oxide (NO x) be converted into soluble nitrogen dioxide (NO 2);
Then, flue gas is sent in absorption tower with the pollutant in alkali liquor absorption flue gas, the sedimentary absorption liquid that obtains sodium sulfite, sodium sulphate and sodium nitrate solution and contain heavy metal Hg; Filter absorption liquid, the sediment that contains heavy metal Hg obtaining send non-ferrous metals smelting works' comprehensive utilization, extracts valuable metal mercury, and filtrate is sodium sulfite, sodium sulphate and sodium nitrate; Filtrate, through oxidizing tower air oxidation, is oxidized to sodium sulphate by sodium sulfite, obtains sodium sulphate and sodium nitrate solution, the cooling sodium sulphate of separating out; Sodium sulphate send alkaline system to produce alkali lye; Sodium nitrate solution, through evaporation, crystallization, obtains sodium nitrate product and sells outward.
It is characterized in that: the product sodium sulphate in recycling flue gas is made alkali lye (NaOH), realizes recycling of alkali absorption liquid; The processing step of making alkali lye (NaOH) is:
(1) by the bisphenol-A (industrial goods) of the sodium sulphate of 10~20 parts (weight), 204~0 parts (weight), 10~20 parts of (weight) quick limes and 40~150 parts of (weight) water, put into conversion reaction still and carry out conversion reaction, under agitation be warmed up to 40~90 ℃, react 60~180 minutes.
Conversion reaction formula is: Na 2sO 4+ Ca (OH) 2+ H 2a=CaSO 4+ Na 2a+2H 2the reacted reacting liquid filtering of O, then use 20~50 ℃ of water washing calcium sulfate precipitations, obtain bisphenol-A sodium-salt aqueous solution.
(2) at 30~80 ℃, bisphenol-A sodium-salt aqueous solution is inputted in tower from carbonization tower top, then passes into the flue gas that contains carbon dioxide purification at the bottom of tower, and in tower, the pH of solution is 8~10, and relative density is 1.1~1.3, and cessation reaction, obtains carbodiimide solution; Carbodiimide solution is filtered, and the bisphenol-A obtaining reclaims and returns to conversion procedure, obtains the Na of concentration 10%~15% 2cO 3solution.
Carburizing reagent formula is: Na 2a+CO 2+ H 2o=Na 2cO 3+ H 2a
(3) carry out causticizing reaction: quick lime is put into ashing pond, add water-solubleization, obtain 95% calcium hydroxide, more further remove tiny sand grains through spinning liquid desander; By 10%~15% Na 2cO 3solution, by 0.10~0.20 kilogram of every cubic metre of adding calcium hydroxide, after preparing, put into together causticizing reaction still, and constantly stir, be warming up to 80~96 ℃, react 90 minutes, when solution concentration is 10% left and right (relative density approximately 1.09~1.1), stop reaction, filtration obtains precipitation of calcium carbonate and alkali lye (NaOH) through washing, and alkali lye (NaOH) is got back to the utilization of smoke absorption systemic circulation as absorption liquid, and precipitation of calcium carbonate recoverable is produced quick lime or as building materials.
Causticizing reaction formula is: Na 2cO 3+ Ca (OH) 2=2NaOH+CaCO 3.
CN201310297877.7A 2013-07-06 2013-07-06 Flue gas purifying method with recyclable alkali absorption liquid Pending CN103585869A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669427A (en) * 2016-02-26 2016-06-15 程洪光 Recover method for acid mist generated by acid hydrolysis reaction in citric acid production
CN109694955A (en) * 2019-02-20 2019-04-30 湘潭大学 A kind of pre- sulfur method of lead plaster based on the double alkali of sodium calcium
CN110330038A (en) * 2019-04-10 2019-10-15 水口山有色金属有限责任公司 A method of the harmless treatment of alum containing beryllium

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5316357A (en) * 1976-07-30 1978-02-15 Ishikawajima Harima Heavy Ind Co Ltd Wet type desulfurization and denitrification method for exhausted smoke
CN1042524A (en) * 1989-10-27 1990-05-30 太原机械学院 The manufacture method of alkaline carbonate
CN1923341A (en) * 2006-08-23 2007-03-07 浙江大学 Device and method for coal-burning boiler fume ozone oxidation and simultaneous desulfurization and denitrification
CN1923337A (en) * 2006-08-23 2007-03-07 浙江大学 Boiler smoke gas multipollutant ozonization and simultaneous elimination device and method therefor
CN101053747A (en) * 2007-04-30 2007-10-17 武汉凯迪电力环保有限公司 Simultaneously desulfurization and denitration wet ammonia flue gas cleaning technology and system thereof
CN102847430A (en) * 2012-08-10 2013-01-02 艾淑艳 System and technology for cleaning flue gas

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5316357A (en) * 1976-07-30 1978-02-15 Ishikawajima Harima Heavy Ind Co Ltd Wet type desulfurization and denitrification method for exhausted smoke
CN1042524A (en) * 1989-10-27 1990-05-30 太原机械学院 The manufacture method of alkaline carbonate
CN1923341A (en) * 2006-08-23 2007-03-07 浙江大学 Device and method for coal-burning boiler fume ozone oxidation and simultaneous desulfurization and denitrification
CN1923337A (en) * 2006-08-23 2007-03-07 浙江大学 Boiler smoke gas multipollutant ozonization and simultaneous elimination device and method therefor
CN101053747A (en) * 2007-04-30 2007-10-17 武汉凯迪电力环保有限公司 Simultaneously desulfurization and denitration wet ammonia flue gas cleaning technology and system thereof
CN102847430A (en) * 2012-08-10 2013-01-02 艾淑艳 System and technology for cleaning flue gas

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669427A (en) * 2016-02-26 2016-06-15 程洪光 Recover method for acid mist generated by acid hydrolysis reaction in citric acid production
CN109694955A (en) * 2019-02-20 2019-04-30 湘潭大学 A kind of pre- sulfur method of lead plaster based on the double alkali of sodium calcium
CN110330038A (en) * 2019-04-10 2019-10-15 水口山有色金属有限责任公司 A method of the harmless treatment of alum containing beryllium

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