WO2015185000A1 - 一种烟道气脱硫脱硝工艺及设备 - Google Patents

一种烟道气脱硫脱硝工艺及设备 Download PDF

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WO2015185000A1
WO2015185000A1 PCT/CN2015/080761 CN2015080761W WO2015185000A1 WO 2015185000 A1 WO2015185000 A1 WO 2015185000A1 CN 2015080761 W CN2015080761 W CN 2015080761W WO 2015185000 A1 WO2015185000 A1 WO 2015185000A1
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desulfurization
denitration
flue gas
tower
solution
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PCT/CN2015/080761
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English (en)
French (fr)
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魏雄辉
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魏雄辉
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Priority to JP2017516022A priority Critical patent/JP6293977B2/ja
Application filed by 魏雄辉 filed Critical 魏雄辉
Priority to CA2952395A priority patent/CA2952395C/en
Priority to AU2015271405A priority patent/AU2015271405B2/en
Priority to ES15803247T priority patent/ES2895874T3/es
Priority to PL15803247T priority patent/PL3153224T3/pl
Priority to EP15803247.4A priority patent/EP3153224B1/en
Priority to EA201692275A priority patent/EA038253B1/ru
Priority to US15/314,632 priority patent/US9895661B2/en
Priority to KR1020177000354A priority patent/KR101871197B1/ko
Priority to BR112016028200-0A priority patent/BR112016028200B1/pt
Priority to MX2016016126A priority patent/MX2016016126A/es
Publication of WO2015185000A1 publication Critical patent/WO2015185000A1/zh
Priority to ZA2016/08885A priority patent/ZA201608885B/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C01B17/60—Isolation of sulfur dioxide from gases
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1456—Removing acid components
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
    • B01D53/14—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 by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • 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
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • 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
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/202—Alcohols or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0001—Separation or purification processing
    • C01B2210/0003—Chemical processing
    • C01B2210/0007—Chemical processing by complexation
    • 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

Definitions

  • the invention relates to the field of gas desulfurization and denitration industry, in particular to a process and equipment for flue gas or various combustion tail (waste) gas desulfurization and denitrification.
  • Fossil fuel combustion produces a large amount of flue gas that is released into the atmosphere.
  • flue gas In addition to sulfur dioxide, sulfur trioxide, hydrogen chloride, hydrogen fluoride, nitrogen oxides and a small amount of harmful organic matter, it also contains a large amount of dust, and the slight hydrophilicity of these dusts.
  • non-hydrophilic particles mainly calcium salt particles, aluminum salt particles, magnesium salt particles, titanium salt particles, iron salt particles, lead salt particles, zinc salt particles, cobalt salt particles, rare earth element particles, radioactive element particles, and others
  • Harmful element particles as well as mineral particles such as silica particles, mullite particles, silicate particles, phosphate particles; these particles are emitted into the atmosphere together with the flue gas, and the surface of these particles is easy to adsorb sulfur dioxide, Sulfur trioxide, hydrogen chloride, hydrogen fluoride, nitrogen oxides, harmful organic matter and bacteria, etc., cause a significant increase in the content of atmospheric suspended particles (this is commonly referred to as PM100, PM10, PM2.5, etc.), causing haze and atmospheric photochemistry.
  • the reaction phenomenon causes serious environmental pollution.
  • Flue gas desulfurization and denitrification processes are now independent of each other, usually denitrification and then desulfurization.
  • the current desulfurization process mainly includes furnace desulfurization process of flue gas injection, flue gas, dry desulfurization process of sulfur-containing industrial raw material gas and other waste gas, and wet desulfurization process.
  • the furnace calcination method is a process for desulfurization in the combustion process, and is a method for directly depositing an oxide or carbonate containing calcium or magnesium into the boiler furnace to fix sulfur, or An oxide or carbonate of calcium or magnesium is directly mixed with coal to be uniformly fed into a furnace for combustion of sulfur; these oxides or carbonates containing calcium or magnesium are sulphur dioxide or trioxide formed by combustion. Sulfur reacts at high temperature to produce calcium sulfate or magnesium sulfate, and also produces calcium sulfite or magnesium sulfite. These sulfites are partially oxidized by oxygen in the flue gas to calcium sulfate or magnesium sulfate to fix some of the sulfur in the combustion.
  • the desulfurization efficiency is not high, usually less than 80%; and the Ca/S (Mg/S) ratio is much larger than 1.5, and the resource of the oxide or carbonate containing calcium or magnesium is very expensive.
  • the dry desulfurization process is followed by a dry desulfurizer before the flue gas is vented, and then vented after desulfurization.
  • the dry desulfurizer is filled with a solid particle dry desulfurizer, and the dry desulfurizer usually has iron oxide, zinc oxide, manganese oxide, cobalt oxide, chromium oxide and molybdenum oxide. These dry desulfurizers absorb the flue gas. Sulfur dioxide produces the corresponding sulfites, and when these oxides lose their ability to absorb sulfur dioxide, they are replaced with new dry desulfurizers. Dry desulfurizers are extremely expensive, and The price is expensive, and at the same time, a large amount of waste residue needs to be piled up and landfill, which will cause serious pollution transfer and secondary pollution.
  • the wet desulfurization process includes limestone wet desulfurization process, lime wet desulfurization process, ammonia desulfurization process, double alkali desulfurization process, ammonium phosphate desulfurization process, wet magnesium desulfurization process, seawater desulfurization process, and Wellman- Wellman-Lord desulfurization process, sodium sulfite (or potassium) desulfurization process and organic acid-organic acid salt buffer solution desulfurization process.
  • the limestone wet desulfurization process is that the calcium carbonate stone from the mine is crushed by a crusher, and then ground into a fine powder having a mesh number of more than 325 mesh by a ball mill, and then formulated into a slurry containing 10% to 15% of calcium carbonate powder;
  • the calcium slurry is in countercurrent contact with the flue gas in the desulfurization tower (may also be in downstream flow, or in countercurrent and cocurrent mixing), the sulfur dioxide in the gas reacts with the calcium carbonate in the slurry to form calcium sulfite; the calcium carbonate slurry is converted into calcium sulfite.
  • the slurry, the calcium sulfite slurry is oxidized into calcium sulfate in the air forced oxidation layer of the desulfurization tower, and the calcium sulfite slurry is converted into the calcium sulfate slurry; the calcium sulfate slurry flows out of the desulfurization tower, and enters the separator to separate the calcium sulfate in the slurry; The water is returned for the preparation of the calcium carbonate slurry for recycling; the separated calcium sulfate is either used as a residue for landfill or road repair, or is purified for use in the manufacture of gypsum board.
  • the calcium carbonate slurry contains tiny hydrophilic and non-hydrophilic particles (mainly calcium salt particles, aluminum salt particles, magnesium salt particles, titanium salt particles, iron salt particles, lead salt particles, zinc salt particles, Cobalt salt particles, rare earth element particles, radioactive element particles and other harmful element particles, and mineral particles such as silica particles, mullite particles, silicate particles, phosphate particles, etc.
  • tiny hydrophilic and non-hydrophilic particles mainly calcium salt particles, aluminum salt particles, magnesium salt particles, titanium salt particles, iron salt particles, lead salt particles, zinc salt particles, Cobalt salt particles, rare earth element particles, radioactive element particles and other harmful element particles, and mineral particles such as silica particles, mullite particles, silicate particles, phosphate particles, etc.
  • the lime wet desulfurization process uses the calcined calcium oxide to react with water to form a calcium hydroxide aqueous emulsion, which is formulated into a slurry containing 10% to 15% of calcium hydroxide; the calcium hydroxide slurry is in the desulfurization tower and the smoke
  • the gas is countercurrently contacted (also in downstream flow, or in countercurrent and downstream mixing).
  • the sulfur dioxide in the gas reacts with the calcium hydroxide in the slurry to form calcium sulfite, and the calcium hydroxide slurry is converted into a calcium sulfite slurry; the calcium sulfite slurry
  • the forced oxidation layer of the air in the desulfurization tower is oxidized to calcium sulfate, and the calcium sulfite slurry is converted into a calcium sulfate slurry;
  • the calcium sulfate slurry flows out of the desulfurization tower, and enters the separator to separate the calcium sulfate in the slurry; the separated water is returned for preparation.
  • the calcium hydroxide slurry is recycled; the separated calcium sulfate is either used as a waste residue for landfill or road repair, or is purified for use in the manufacture of gypsum board.
  • the process produces a lot of solid calcium sulfate, which also contains solid waste such as calcium sulfite, calcium carbonate and unreacted calcium hydroxide.
  • the lime consumption is large, the equipment is huge, and the investment is large.
  • there is solid sediment which is easy to cause equipment blockage, sewage discharge is more, secondary pollution is more serious;
  • a large amount of coal is consumed, and serious Pollution.
  • the calcium hydroxide slurry contains tiny hydrophilic and non-hydrophilic particles (mainly calcium salt particles, aluminum salt particles, magnesium salt particles, titanium salt particles, iron salt particles, lead salt particles, zinc salt particles). Cobalt salt particles, rare earth element particles, radioactive element particles and other harmful element particles, and mineral particles such as silica particles, mullite particles, silicate particles, phosphate particles, etc.
  • the ammonia desulfurization process uses a certain concentration of ammonia water as an absorbent to absorb sulfur dioxide in the flue gas, react to form ammonium hydrogen sulfite, and then be forcibly oxidized to ammonium hydrogen sulfate. The ammonium hydrogen sulfate is finally alkalized to ammonium sulfate by ammonia. Ammonium sulfate is separated as a by-product of fertilizer.
  • the process is that the flue gas after heat exchange between the dust removal and the gas heat exchanger is in contact with the ammonia water in the desulfurization tower or in the form of a countercurrent or countercurrent and downstream flow, and the sulfur dioxide in the flue gas is converted into ammonia by the ammonia water absorption.
  • Ammonium hydrogen sulfate the flue gas after desulfurization is exchanged by the gas heat exchanger and discharged into the atmosphere through the chimney; the ammonium hydrogen sulfite solution produced after desulfurization is subjected to a forced oxidation section in the desulfurization tower or a separate forced oxidizer After being oxidized by air or ozone, it is converted into ammonium hydrogen sulfate, and then converted into ammonium sulfate by alkalization with ammonia gas or concentrated ammonia water, and crystallized by a crystallizer, separated and dried to obtain ammonium sulfate fertilizer by-product; separated ammonia water.
  • the mother liquor continues to be blended with ammonia, increasing the concentration of ammonia and continuing to recycle.
  • the ammonia desulfurization process has high desulfurization efficiency and small solution circulation; however, ammonia is highly toxic, extremely volatile, and has a low boiling point.
  • the phenomenon of entrained ammonia in the flue gas is serious, causing a large amount of ammonia loss and causing secondary pollution of atmospheric ammonia.
  • ammonia desulfurization process consumes a large amount of ammonia, ammonia is converted into low-value ammonium sulfate, the desulfurization cost is high, and it is easy to produce crystallization blockage equipment and pipelines; and ammonia is highly corrosive, equipment corrosion is serious, and ammonia production
  • the process is a process of high energy consumption and high pollution. Excessive consumption of ammonia is also a process of indirectly increasing environmental pollution and increasing energy consumption, so the use of ammonia should be minimized.
  • the double alkali desulfurization process is to absorb sulfur dioxide in the flue gas in a desulfurization tower by using an aqueous solution of a water-soluble alkaline metal salt such as NaOH or Na 2 CO 3 or Na 2 SO 3 to form a water-soluble reaction.
  • a water-soluble alkaline metal salt such as NaOH or Na 2 CO 3 or Na 2 SO 3
  • the double alkali desulfurization process is to avoid the precipitation blockage problem of the pure limestone (or lime) process, but the limestone (or lime) is actually used as the desulfurizer.
  • the ammonium phosphate fertilizer desulfurization process is a desulfurization technology and process for directly producing ammonium phosphate composite fertilizer in the flue gas desulfurization process by using natural phosphate ore and ammonia as raw materials.
  • the process mainly consists of unit operations such as adsorption, extraction, neutralization, absorption, oxidation, concentration and drying.
  • Adsorption is the use of activated carbon as the first-stage desulfurization adsorption medium to adsorb SO 2 in the flue gas. Under the condition of oxygen, SO 2 is catalytically oxidized to SO 3 . When the adsorption capacity of activated carbon is close to saturation, the activated carbon is washed and regenerated.
  • dilute sulfuric acid can be obtained, the concentration thereof is more than 30%, and the activated carbon is repeatedly used;
  • the phosphoric acid for extracting phosphate rock is to react the dilute sulfuric acid prepared by primary desulfurization with the phosphate rock (Ca 10 (PO 4 ) F 2 ) powder. Producing hydrogen fluoride, phosphoric acid and calcium sulfate; extracting and filtering to obtain phosphoric acid, the extraction ratio of phosphate rock is greater than 90%, and the concentration of dilute phosphoric acid is greater than 10 to 14%; neutralization is to react ammonia with extracted phosphoric acid to prepare diammonium phosphate.
  • Diammonium hydrogen phosphate is used as a secondary desulfurizer, and diammonium phosphate absorbs SO 2 in a second-stage desulfurization tower to form diammonium hydrogensulfite and ammonium dihydrogen phosphate; oxidation is to oxidize diammonium hydrogen sulfite in solution to sulfuric acid Ammonium, oxidized solution, concentrated and dried solid ammonium dihydrogen phosphate and ammonium sulfate compound fertilizer.
  • the process is very complicated, with large investment, large steam consumption and high energy consumption. At the same time, it needs to consume a large amount of natural phosphate rock, so the technology and process are not applicable anywhere, only natural phosphate rock can be used. .
  • the wet magnesium desulfurization process is a slurry of magnesium oxide or magnesium hydroxide in countercurrent contact with the flue gas in the desulfurization tower (also in downstream flow, or in countercurrent and cocurrent mixing), sulfur dioxide in the gas and magnesium oxide or hydrogen in the slurry.
  • the magnesium oxide reacts to form magnesium sulfite; the magnesium oxide or magnesium hydroxide slurry is converted into a magnesium sulfite slurry, and the magnesium sulfite slurry is precipitated, and the separator is separated into magnesium sulfate in the slurry; the separated water is returned for preparation of oxidation.
  • the magnesium or magnesium hydroxide slurry is recycled; the separated magnesium sulphate is calcined above 1235K to produce magnesium oxide and gaseous sulfur dioxide, and the produced magnesium oxide is reused, and the sulfur dioxide can be recovered.
  • the solid magnesium sulphate produced by the process is easy to block the pipeline and equipment.
  • the magnesium sulphite is calcined above 1235K to decompose, the energy consumption is high, the investment is large, and the secondary pollution is serious.
  • magnesium oxide or magnesium hydroxide slurry contains tiny hydrophilic and non-hydrophilic particles (mainly calcium salt particles, aluminum salt particles, magnesium salt particles, titanium salt particles, iron salt particles, lead salt particles, Zinc salt particles, cobalt salt particles, rare earth element particles, radioactive element particles and other harmful element particles, and mineral particles such as silica particles, mullite particles, silicate particles, phosphate particles, etc.
  • tiny hydrophilic and non-hydrophilic particles mainly calcium salt particles, aluminum salt particles, magnesium salt particles, titanium salt particles, iron salt particles, lead salt particles, Zinc salt particles, cobalt salt particles, rare earth element particles, radioactive element particles and other harmful element particles, and mineral particles such as silica particles, mullite particles, silicate particles, phosphate particles, etc.
  • the seawater desulfurization process utilizes a salt containing a large amount of calcium, magnesium, aluminum, sodium, potassium, etc. in seawater, especially a carbonate, which has a high alkalinity.
  • This method of directly absorbing sulfur dioxide in flue gas by seawater is a seawater desulfurization method.
  • the process is very simple. In the desulfurization tower, seawater and flue gas are in direct contact, absorbing sulfur dioxide in the flue gas, and alkali in seawater.
  • Sex substances especially carbonates; in order to increase the alkalinity of seawater, sometimes artificially add calcium oxide or calcium hydroxide to seawater
  • sulfur dioxide to produce sulfite
  • the sulfite is oxidized to sulfate and then discharged directly into the sea.
  • This technology and process can only be applied at the seaside because of the large consumption of sea water. Because a large amount of sulphate is discharged into the sea, it will cause damage to the seawater environment more or less.
  • the sodium sulfite (or potassium) desulfurization process is similar to the wet magnesium desulfurization process, in which a sodium sulfite (or potassium) aqueous solution is countercurrently contacted with the flue gas in a desulfurization tower (also in downstream flow, or in countercurrent and downstream mixing).
  • Sulfur dioxide in the gas reacts with sodium sulfite (or potassium) in the solution to form sodium hydrogen sulfite (or potassium); sodium sulfite (or potassium) solution is converted into sodium bisulfite (or potassium) solution, sodium hydrogen sulfite (or potassium) solution It is regenerated in a steam heating regenerator, and the sodium hydrogen sulfite (or potassium) solution is converted into an aqueous solution of sodium sulfite (or potassium), and sulfur dioxide is released. The sodium sulfite (or potassium) aqueous solution is recycled, and the sulfur dioxide gas can be recovered as a by-product.
  • the Wellman-Lord desulfurization process is actually an improved sodium sulfite cycle process, except that a multi-effect evaporation process is added to the sodium sulfite cycle process to evaporate the desulfurization solution to crystallize sodium sulfite.
  • the method has large-scale application examples in the United States, Germany, France, and Japan, but its steam consumption is large and energy consumption is high.
  • the organic acid-organic acid salt buffer solution desulfurization process uses a buffer solution composed of an organic acid and an organic acid salt as a desulfurization liquid, and is in countercurrent contact with the flue gas in the desulfurization tower (may also be in downstream flow, or in a countercurrent and downstream mixed contact).
  • the sulfur dioxide in the gas reacts with the organic acid salt in the solution to form bisulfite and organic acid; the solution is regenerated in a steam heating regenerator, the sulfite in the solution is converted into an organic acid salt, and the solution is still converted into an organic acid.
  • An organic acid salt buffer solution which is reused and simultaneously releases sulfur dioxide, which can be recovered as a by-product.
  • the denitration process currently used in actual production is a catalytic ammonia denitration process.
  • Ammonia is catalytic denitration process at a temperature of about 150 °C ⁇ 500 °C and under conditions of catalyst, ammonia is injected directly into the flue gas in the catalyst layer, the reaction of ammonia and NO X N 2 and H 2 O to reach the purpose of the elimination of NO X.
  • the process ammonia consumption amount is large, since the flue gas contains from about 4% to 9% of O 2, O 2, and ammonia will react NO X and ammonia is consumed, ammonia, while the reaction is not complete, some ammonia and flue
  • the gas is discharged into the atmosphere together to increase the loss of ammonia and cause secondary pollution.
  • a large amount of fossil fuel is consumed, and a large amount of waste gas, waste residue and waste water are generated, which is a serious environmental pollution process, so the use of ammonia should be avoided as much as possible.
  • the flue gas desulfurization and denitration process and the desulfurization and denitration solution used in the equipment are complex solutions containing polyols (and/or polyalcohols); composition, content and characteristics of these desulfurization and denitration solutions It has been described in our patented technology and will not be described here.
  • an appropriate additive may be added to the desulfurization and denitration solution containing the polyalcohol (and/or polyalcohol-containing); to the desulfurization and denitration solution
  • What additives are added, as well as the composition, content and characteristics of the additives, have also been described in our patented technology and will not be described here.
  • the flue gas desulfurization and denitration process and equipment of the invention have the functions of simultaneous desulfurization and denitrification, and the principle of desulfurization thereof has been described in our patented technology, and will not be described here; only the principle of denitration is described as follows:
  • Denitration are mainly nitrogen oxide removal in the flue gas NO X (x refers to the number of oxygen atoms) (nitrogen oxides including NO 2, NO, N 2 O, etc., more than 90% of the flue gas is NO).
  • the composition of the desulfurization and denitration solution is composed of EG (ethylene glycol) and/or PEG (polyethylene glycol), water, polycarboxylic acids and/or polycarboxylates and additives.
  • the esterification mechanism and denitration mechanism of the desulfurization and unsalable solution of the present invention are illustrated by taking only ethylene glycol, citric acid and salts thereof and a sulfone group-containing substance as an example. It is not limited to the desulfurization and denitration solution of the present invention, which is composed only of ethylene glycol, citric acid and salts thereof and substances containing sulfone and/or sulfoxide groups, but is composed of ethylene glycol and/or polyethylene glycol.
  • Organic acids and / or organic acid salts and additives (already listed in our patented technology, here The desulfurization and unsalted solution of the composition is not listed.
  • the desulfurization and denitration solution after regeneration is recycled.
  • sulfoxide and/or sulfone group-containing additives such as DMSO and/or sulfolane, or their hydroxyl and/or carboxyl substituents
  • sulfoxide and/or sulfone group-containing additives such as DMSO and/or sulfolane, or their hydroxyl and/or carboxyl substituents
  • the flue gas desulfurization and denitration process of the invention comprises: waste heat recovery, desulfurization and denitration, regeneration of desulfurization and denitration solution, and key processes of sulfur dioxide and NO X enrichment.
  • Waste heat recovery process The temperature of the flue gas is reduced to below 50 °C by heat exchange recovery method, and waste heat recovery is performed.
  • waste heat recovery process Since flue gas is usually smoked at a temperature of 130 ° C to 170 ° C and has a large amount of smoke, it contains considerable sensible heat and latent heat (heat contained in water vapor in the flue gas). The process of reducing the flue gas from 130 ° C to 170 ° C to below 50 ° C and trying to recover this part of the heat is called the waste heat recovery process.
  • the method of waste heat recovery usually has the methods of indirect heat recovery, direct heat recovery, indirect heat transfer and direct heat recovery.
  • the indirect heat exchange recovery method is in the wall-tube heat exchanger, the hot flue gas goes to the side of the heat exchange wall, and the other side of the heat storage fluid moves away, the flue gas and the heat storage fluid do not contact each other, and the heat storage fluid passes through
  • the wall surface heat conduction indirectly cools the temperature of the flue gas, and the temperature of the heat storage fluid increases.
  • the direct heat exchange mode is in the direct heat exchanger, and the heat storage fluid is in direct contact with the flue gas (either countercurrent contact or Is the downstream contact), the temperature of the flue gas is cooled, and the temperature of the regenerative fluid is increased; the way of indirect heat exchange and direct heat transfer is simultaneously recovered in the process of waste heat recovery, which has both direct heat recovery and recovery methods.
  • the heat storage fluid described herein is a liquid, preferably a high boiling point, non-volatile, water-incompatible liquid, such as silicone oil, stone sodium oil, high boiling point fatty oil, etc.;
  • the heat storage fluid described herein may be either a liquid or a gas.
  • the high-temperature heat storage fluid that absorbs heat from the flue gas can be used as a heat source for heating the boiler's make-up water, or for heating in any other place where heating is required.
  • Desulfurization and denitration process in the absorption tower, the sulfur dioxide and/or nitrogen oxides in the flue gas or various combustion tail (waste) gas are absorbed by the desulfurization and denitration solution, and the desulfurization and denitration solution is a polyol-containing and/or nitrogen oxide.
  • the flue gas with a temperature lower than 50 °C is directly contacted with the desulfurization and denitration solution (commonly referred to as "desulfurization and denitrification lean liquid") in the absorption tower, and the sulfur dioxide in the flue gas is absorbed by the desulfurization and denitration solution, and at the same time, the flue
  • the nitrogen oxides and carbon dioxide in the gas are also partially absorbed by the desulfurization and denitration solution, and then the desulfurization and denitration solution is converted into a “desulfurization and denitration rich liquid”, and the desulfurization and denitration rich liquid flows out of the absorption tower and is sent to the desulfurization and denitration solution regeneration process.
  • the flue gas purified by desulfurization and denitrification (the temperature is preferably 5 ° C higher than the ambient temperature) is discharged into the atmosphere through the chimney.
  • the principle of the absorption of sulfur dioxide by the desulfurization and denitration solution in the desulfurization and denitration process has been described in considerable detail in our patented technology and will not be described here.
  • Desulfurization and denitration solution regeneration process the desulfurization and denitration rich liquid which absorbs sulfur dioxide and/or nitrogen oxides releases sulfur dioxide and/or nitrogen oxides in the regeneration tower by heating and/or stripping and/or vacuum regeneration, and regenerates The post-desulfurization and denitration solution is recycled.
  • the desulfurization and denitration rich liquid sent from the desulfurization and denitration process has a low temperature, and is indirectly exchanged with the desulfurized and denitrated lean liquid flowing out from the bottom of the regeneration tower (usually through a tubular heat exchanger), and then heated to Above 90 ° C, then enter from the upper end of the regeneration tower, in the regeneration tower, the desulfurization and denitration rich liquid and the hot gas for stripping at the bottom (the gas for gas extraction may be an inert gas such as nitrogen, argon or water vapor, temperature
  • the saturated steam temperature corresponding to the water corresponding to the pressure in the regeneration tower is sufficiently countercurrently contacted, and the sulfur dioxide, nitrogen oxides and carbon dioxide dissolved in the desulfurization and denitration rich liquid are analyzed, and mixed with the gas for gas extraction to form a mixed gas, the mixing
  • the gas comes out from the top of the regeneration tower and is sent to the enrichment process for concentration treatment; the desulfurized and denitrated rich liquid after regeneration becomes des
  • the heating and stripping method is used to regenerate the desulfurization and denitration solution, so it is called a stripping and heating desulfurization and denitration solution regeneration tower (or desulfurization and denitration solution regenerator), which is a binary regenerator.
  • the vacuum pumping method is adopted to make the desulfurization and denitration solution regeneration tower have a certain degree of vacuum, and at the same time, the gas extraction, heating and vacuum are used to regenerate the desulfurization and denitration solution, so it is called stripping.
  • heating and vacuum desulfurization denitration solution regeneration tower (or desulfurization denitration solution regenerator) is a three-way regenerator.
  • a super-wave regeneration system and/or a microwave regeneration system and/or a radiation regeneration system may be installed in the desulfurization and denitration solution regeneration tower (or the desulfurization and denitration solution regenerator) to form a gas stripping, heating,
  • a multi-stage desulfurization denitration solution regeneration tower (or a desulfurization and denitration solution) such as vacuum and ultra-wave and/or microwave and/or radiation is a multi-component regenerator.
  • Sulfur dioxide and/or nitrogen oxide enrichment process The released sulfur dioxide and/or nitrogen oxides are concentrated by a concentration column into a higher purity sulfur dioxide gas (or liquid) product and/or a nitrogen oxide gas product.
  • the mixed gas released from the desulfurization and denitration solution regeneration process enters from the middle section of the concentration tower, and is condensed under the top of the concentration tower.
  • the countercurrent contact of the water condenses the water vapor in the mixed gas, and the mixed gas for removing the water vapor flows out from the top of the concentration tower, the gas mainly contains sulfur dioxide component, and also contains some components such as nitrogen oxides and carbon dioxide, among which sulfur dioxide It can be further compressed, cooled and processed into pure liquid sulfur dioxide, or reduced to sulfur by coke, or processed into sulfuric acid.
  • the nitrogen oxide can be used for reduction to nitrogen or as a raw material for nitric acid, and the remaining gas can be returned to the desulfurization and denitration process.
  • Venting water vapor enters from the bottom end of the concentration tower, and is in countercurrent contact with the condensed water.
  • the water vapor raises harmful components such as sulfur dioxide and nitrogen oxides in the condensed water to achieve concentration of sulfur dioxide and nitrogen oxides.
  • the harmful components such as sulfur dioxide and nitrogen oxides in the condensed water are removed, the condensed water is turned into distilled water, flows out from the bottom of the concentration tower, and is recycled to the boiler water.
  • the corresponding key equipments in the flue gas desulfurization and denitration process and equipment of the invention are: a waste heat recovery tower (or waste heat recovery unit), an absorption tower, a regeneration tower and a concentration tower, wherein:
  • Waste heat recovery tower used to exchange heat between flue gas and heat storage fluid, reduce the temperature of flue gas to below 50 °C, and carry out waste heat recovery;
  • Absorption tower used for directly contacting the cooled flue gas with the desulfurization and denitration solution, and the desulfurization and denitration solution absorbs sulfur dioxide and/or nitrogen oxides in the flue gas into a desulfurization and denitration rich liquid, and then is discharged from the absorption tower; the desulfurization
  • the denitration solution is a composite solution containing polyols and/or polyalcohols;
  • Regeneration tower used to desulfurize and denitrate rich liquid by heating and/or stripping and/or vacuum regeneration to analyze sulfur dioxide and/or nitrogen oxides into desulfurization and denitrification lean liquid, and the regenerated desulfurization and denitration liquid is returned to the absorption tower. Recycling;
  • Concentration tower The water vapor in the mixed gas containing sulfur dioxide and/or nitrogen oxides used to regenerate the desulfurization and denitration rich liquid in the regeneration tower is removed by condensation, and the sulfur dioxide and/or nitrogen oxides are concentrated to a higher concentration. Purity of sulfur dioxide and / or nitrogen oxide gas or liquid products.
  • waste heat recovery tower may be provided with one or more stages of waste heat recovery internal circulation pump to increase the circulation amount of the heat storage fluid; the absorption tower may also be provided with one or more stages of desulfurization and denitration internal circulation pump to increase desulfurization The amount of denitration solution circulating.
  • a heat exchanger is disposed between the absorption tower and the regeneration tower, and the desulfurization and denitration rich liquid from the absorption tower and the desulfurization and denitration lean liquid flowing out from the regeneration tower are indirectly heat exchanged through the heat exchanger.
  • FIG. 1 the process and equipment for desulfurization and denitration, desulfurization and denitration solution regeneration, and sulfur dioxide and/or nitrogen oxide enrichment in the flue gas desulfurization and denitration process and equipment are shown in FIG. 1 .
  • the flue gas desulfurization and denitration process of the present invention and the waste heat recovery process and equipment in the apparatus are preferably two, as shown in Figs. 2 and 3, respectively.
  • the invention Compared with the traditional wet desulfurization process (such as calcium desulfurization process, ammonia desulfurization process, etc.), the invention has the following advantages: 1 When the conventional wet desulfurization process is used for flue gas desulfurization, the by-product is calcium sulfate. And calcium sulfite, or ammonium sulfate and ammonium sulfite, the by-product of the flue gas desulfurization and denitration process and equipment of the present invention is high-purity sulfur dioxide, these by-products are important chemical raw materials, have a wide market and important applications.
  • the traditional wet desulfurization process (such as calcium desulfurization process, ammonia desulfurization process, etc.) used in the desulfurizer is calcium carbonate, calcium oxide and / or ammonia; when using calcium carbonate as a desulfurizer, it needs to consume a lot of carbonic acid Calcium, the exploitation of calcium carbonate will seriously damage the environment, causing soil erosion, landslides and ecological environment damage; when using calcium oxide as a desulfurizer, it needs to consume a large amount of calcium oxide, which is obtained by calcination of calcium carbonate and coal.
  • the traditional wet desulfurization process such as calcium desulfurization process, ammonia desulfurization process, etc.
  • the flue gas of the present invention The desulfurization and denitration process corresponding to the desulfurization and denitration process and equipment is a high boiling point, non-toxic, harmless and safe organic polyol polyester solvent, which is used in a full cycle without the consumption of calcium carbonate and/or calcium oxide.
  • the slurry contains tiny hydrophilic and non-hydrophilic Particles (mainly calcium salt particles, aluminum salt particles, magnesium salt particles, titanium salt particles, iron salt particles, lead salt particles, zinc salt particles, cobalt salt particles, rare earth element particles, radioactive element particles, and other harmful element particles, Mineral particles such as silica particles, mullite particles, silicate particles, and phosphate particles are discharged into the atmosphere together with flue gas, and the surface of these particles is easily adsorbed with sulfur dioxide, sulfur trioxide, and chlorine.
  • hydrophilic and non-hydrophilic Particles mainly calcium salt particles, aluminum salt particles, magnesium salt particles, titanium salt particles, iron salt particles, lead salt particles, zinc salt particles, cobalt salt particles, rare earth element particles, radioactive element particles, and other harmful element particles
  • Mineral particles such as silica particles, mullite particles, silicate particles, and phosphate particles are discharged into the atmosphere together with flue gas, and the surface of these particles is easily adsorbed with sulfur dioxide, sulfur trioxide, and chlorine.
  • the flue gas desulfurization and denitration process and equipment of the invention have low operation cost, high desulfurization and denitration efficiency, and at the same time convert waste into valuable chemical raw materials, which can generate a large economy.
  • Benefits, social benefits and environmental benefits; 5 traditional wet desulfurization process will produce insoluble calcium or ammonium salt precipitation during the entire desulfurization and regeneration process, causing blockage of equipment and pipelines.
  • the flue gas desulfurization and denitration process and equipment of the present invention are not Will produce insoluble calcium or ammonium salt precipitation; 6 traditional wet desulfurization process is only suitable for lower sulfur content gas
  • the body flue gas desulfurization and denitration process and equipment of the invention can be used for desulfurization and denitration of low sulfur content gas, and also for desulfurization and denitrification of high sulfur content gas.
  • the flue gas desulfurization and denitration process of the invention and the desulfurization and denitration of the equipment have high purification degree, and the total sulfur content in the gas can be stably reduced to below 50 mg/m 3 , and the boiling point of the solution is high, the loss is small, and the desulfurization and denitration are performed.
  • the flue gas desulfurization and denitration process and equipment of the invention have wide industrial use, and can be used for simultaneously removing sulfur dioxide and nitrogen oxides in gas, and can also be used for separately removing sulfur dioxide from gas or separately removing gas.
  • Nitrogen oxides which can be used in flue gas, incineration gas, coke oven gas, dye plant synthesis waste gas, chemical fiber plant sewage, and other industrial feed gas or exhaust gas containing SOx, such as sulfur gas
  • the total sulfur content in the medium is less than 99.9% (volume ratio).
  • 1 is a schematic diagram of a flue gas desulfurization and denitration, desulfurization and denitration solution regeneration, and sulfur dioxide and/or nitrogen oxide enrichment process and equipment.
  • 1 is the flue gas with temperature below 50 °C
  • 2 is the booster fan
  • 3 is the absorption tower
  • 4 is the desulfurization and denitration internal circulation pump
  • 5 is the chimney
  • 6 is the flue gas after desulfurization and denitrification
  • 7 It is desulfurization and denitrification lean liquid
  • 8 is desulfurization and denitration rich liquid
  • 9 is rich liquid pump
  • 10 is desulfurization and denitration pump
  • 11 is lean liquid tank
  • 12 is lean liquid pump
  • 13 is cooler
  • 14 is heat exchanger
  • 15 is Cooling water
  • 16 is hot water
  • 17 is rich liquid heater
  • 18 is heat medium
  • 19 is cold medium
  • 20 is regeneration tower
  • 21 is regeneration analysis gas
  • 22 is steam extraction steam
  • 23 concentration tower
  • 24 It is a distilled water pump
  • 25 is concentrated sulfur dioxide and/or nitrogen oxide gas
  • 26 is distilled water.
  • F 1 , F 2 , F 3 , and F 4 represent the flow rate of the flue gas 1, the flow rate of the desulfurized lean liquid 7, and the steam flow rate into the regeneration tower 20, respectively.
  • a 5 is a content of SO 2 and NO in the regeneration of desulfurization and denitration poor liquid 7
  • a 6 is SO 2 and NO content in the distilled water 26
  • P 1 is The pressure at the bottom of the absorption tower 3
  • P 2 is the pressure at the top of the absorption tower 3
  • P 3 is the pressure in the regeneration tower 20
  • P 4 is the pressure of the steam 22
  • P 5 is the pressure in the concentration tower 23
  • T 1 is the flue gas 1
  • T 2 is the temperature of the flue gas 6 after desulfurization and denitration
  • T 3 is the temperature in the absorption tower 3
  • T 4 is the temperature of the desulfurization and denitration lean liquid 7 entering the absorption tower 3
  • T 5 is the outlet cooler 13 poor liquid temperature desulfurization and denitrification 7, T 6 of the heat exchanger 14 the temperature desulfurization and denitrification lean liquid, T 7 into the heat exchanger 14 to a temperature desulfurization and denitrification of the rich liquid,
  • FIG. 2 is a schematic diagram of a process flow and equipment for a direct heat exchange recovery mode of flue gas waste heat recovery.
  • 27 is the flue gas from the boiler with a temperature of 130-180 °C
  • 28 is the flue gas with the temperature lower than 50 °C after the waste heat recovery
  • 29 is the direct heat recovery waste heat recovery tower
  • 30 is the waste heat recovery inner circulation.
  • Pump 31 is a heat storage fluid
  • 32 is heat storage The fluid pump
  • 33 is a heat storage fluid sink tank
  • 34 is dust and water
  • 35 is a heat storage fluid external circulation pump
  • 36 is a heat storage fluid radiator
  • 37 is a heat storage fluid cooler
  • 38 is a cold heat storage fluid
  • 39 is the heated medium
  • 40 is the heated medium
  • 41 is the cooling water
  • 42 is the hot water.
  • Fig. 3 is a schematic diagram showing the process flow and equipment of the heat recovery mode in which the direct heat exchange and the indirect heat exchange of the flue gas waste heat recovery are simultaneously performed.
  • 27 is the flue gas from the boiler with a temperature of 130-180 ° C
  • 28 is the flue gas with the temperature after the waste heat recovery is lower than 50 ° C
  • 29 is the direct heat recovery waste heat recovery tower
  • 30 is the waste heat recovery.
  • Circulating pump 31 is a thermal heat storage fluid
  • 32 is a heat storage fluid pump
  • 33 is a heat storage fluid sink tank
  • 34 is dust and water
  • 35 is a heat storage fluid external circulation pump
  • 37 is a heat storage fluid cooler
  • 38 is The cold heat storage fluid
  • 39 is the heated medium
  • 40 is the heated medium
  • 41 is the cooling water
  • 42 is the hot water
  • 43 is the flue gas indirect heat exchange heat recovery device.
  • Increasing the number of stages (or stages) of the desulfurization and denitration internal circulation pump 4, and increasing the number of stages (or stages) of the desulfurization and denitration internal circulation pump 4 may be 0, or 1 or 2, or 3, or 4. ..
  • the specific number of stages to be increased can be determined by the sulfur dioxide and / nitrogen oxide content of the flue gas 6 after desulfurization and denitrification at the top outlet of the absorption tower 3; absorption of sulfur dioxide, part
  • the desulfurization and denitration liquid 7 of nitrogen oxides and carbon dioxide is converted into the desulfurization and denitration rich liquid 8, flows out from the bottom of the absorption tower 3, is pressurized by the rich liquid pump 9, and passes through the shell side of the heat exchanger 14 and the regeneration tower 20.
  • the hot desulfurization and denitration liquid 7 is subjected to heat exchange, the temperature is raised, and then passed through the rich medium heater 17 by the heat medium 18 (the heat medium may be a liquid having a temperature of more than 100 ° C or a flue of 130 ° C to 170 ° C).
  • the desulfurization and denitration rich liquid 8 having a temperature of more than 90 ° C enters the regeneration tower 20 from the upper end, and the steam extraction steam 22 enters the regeneration tower 20 from the bottom, and the desulfurization and denitration rich liquid 8 and the stripping in the regeneration tower 20 at a temperature greater than 90 ° C Direct contact with steam 22 is performed.
  • sulfur dioxide, a part of nitrogen oxides and carbon dioxide in the desulfurization and denitration rich liquid 8 are analyzed, and are mixed into the stripping steam 22 to be mixed into the regenerated analytical gas 21 to flow out from the top of the regeneration tower 20, and released.
  • the desulfurization and denitration rich liquid 8 having a temperature of sulfur dioxide, a part of nitrogen oxides and carbon dioxide of more than 90 ° C is converted into a hot desulfurization and denitration liquid 7 having a temperature of more than 90 ° C, flows out from the bottom of the regeneration tower 20, and passes through the heat exchanger 14
  • the heat exchange is performed with the desulfurization and denitration rich liquid 8 sent from the rich liquid pump 9 in the shell side, and the temperature is lowered, and the temperature of the desulfurization and denitration liquid 7 is reduced, and the tube length of the cooler 13 is cooled by the shell cooling water 15 Up to normal temperature, and sent to the lean liquid tank 11 by the lean liquid pump 12, and then the desulfurization and denitration liquid 7 in the lean liquid tank 11 is pressurized by the desulfurization pump 10 and sent to the absorption tower 3 for desulfurization and denitrification, and desulfurization
  • the denitration solution is like this
  • the cooling water 15 is condensed, and the concentrated sulfur dioxide and/or nitrogen oxide gas 25 composed of a mixed gas of sulfur dioxide, nitrogen oxides, and carbon dioxide which are not condensed flows out of the concentration tower 23, and can be recovered as a raw material gas, and the distilled water is condensed at the same time.
  • the sulfur dioxide and the like are contained therein, and continue to flow to the bottom of the concentration tower 23 to be in contact with the stripping steam 22 at the bottom.
  • the sulfur dioxide and the like in the distilled water are extracted by the stripping steam 22, so that the condensed water is substantially free.
  • a gas such as sulfur dioxide reaches the standard of distilled water 26 for recovery, and is sent to a recycling pump 24 for recycling.
  • the cooling water 15 is converted into hot water 16 by heating, and can be recovered as a supplementary hot water for the boiler;
  • the heat medium 18 is converted into a cold medium 19 after releasing heat;
  • the cold medium 19 can be distilled water or other liquid, which can Continue to absorb heat and then convert to heat medium 18 for repeated use; when the cold medium 19 is cooled flue gas, continue to cool to flue gas 1 at a temperature below 50 °C.
  • Fig. 2 The process flow of the direct heat recovery method for flue gas waste heat recovery and the operation mode of the equipment are shown in Fig. 2: the flue gas 27 from the boiler with a temperature of 130-180 ° C enters the direct heat recovery waste heat recovery tower 29 from the bottom. Direct contact with the cold heat storage fluid 38 sprayed from the top of the tower for direct heat exchange, and the flue gas 27 from the boiler with a temperature of 130-180 ° C is cooled and converted into a flue gas 28 having a temperature lower than 50 ° C. It is discharged from the top of the direct heat exchange waste heat recovery tower 29.
  • the number of stages (or stages) of the ring pump 30, the number of stages (or stages) that increase the waste heat recovery internal circulation pump 30 may be 0, or 1 or 2, or 3, or 4... or n
  • the stage (n is a positive integer) or the like, and the number of stages to be specifically increased can be determined by the temperature of the flue gas 28 discharged from the top of the direct heat recovery waste heat recovery tower 29.
  • the cold heat storage fluid 38 absorbs the heat of the flue gas 27 and then converts it into a heat storage fluid 31 whose temperature is close to or lower than the temperature of the flue gas 27, while the cold heat storage fluid 38 It will also contain HCl, HF, and fine dust in the flue gas 27 (including water-soluble and water-insoluble, ie, polar and non-polar micro-particles, also known as PM100 and/or PM50 and/or PM2.5.
  • the various particles are adsorbed and concentrated, part of the water vapor in the flue gas 27 is condensed into water, mixed together in the thermal heat storage fluid 31, and discharged from the bottom of the direct heat recovery waste heat recovery tower 29, and stored.
  • the hot fluid pump 32 is sent to the heat storage fluid sink tank 33 for sedimentation, and the dust and water 34 containing HCl and HF are separated and discharged from the bottom of the heat storage fluid sink tank 33, and the heat storage after dust removal and water removal is performed.
  • the fluid 31 is sent to the heat storage fluid radiator 36 by the heat storage fluid external circulation pump 35, and most of the heat is transferred to the heated medium 39 in the heat storage fluid radiator 36, and the heat is absorbed by the heating medium 39.
  • the medium 40 is heated and used as a heat source to recover heat.
  • the heat storage fluid 31 that has released a portion of the heat is again cooled into the heat storage fluid cooler 37 by the cooling water 41 to be cooled to a normal temperature, and is converted into a cold heat storage fluid 38 and then enters the direct heat treatment waste heat recovery tower 29 for repeated heat absorption.
  • the cooling water 41 absorbs heat and is converted into hot water 42, and the heat therein can be recycled.
  • the temperature of the gas 27 can be recovered as a heat source after being heated; the flue gas 27 which releases part of the heat enters the direct heat recovery waste heat recovery tower 29 from the bottom, and the cold heat storage fluid 38 sprayed from the top of the tower is directly Contact, direct heat exchange, while the flue gas 27 is cooled and converted into a flue gas 28 having a temperature lower than 50 ° C and discharged from the top of the direct heat recovery waste heat recovery tower 29, in order to increase the gas-liquid contact surface, prolong the gas-liquid contact time
  • the number of stages (or stages), the number of stages (or stages) that increase the waste heat recovery internal circulation pump 30 can be 0, or 1 or 2, or 3, or 4 or n (n is The positive integer) and the like, the specific number of stages to be increased may be determined by the temperature of the flue gas 28 discharged from the top of the direct heat recovery waste heat recovery tower 29; in the direct heat exchange waste heat recovery tower 29, the cold heat storage fluid 38 is absorbed. The heat of the flue gas 27 is then converted into a thermal thermal fluid 31 having a temperature near or below the temperature of the flue gas 27 entering the direct heat recovery waste heat recovery column 29 from the bottom, while the cold thermal fluid 38 will also be the flue.
  • HCl, HF, and fine dust in gas 27 (including water-soluble and water-insoluble, ie, polar and non-polar micro-particles, which are commonly referred to as PM100 and/or PM50 and/or PM2.5.
  • the particles are adsorbed and concentrated, and part of the water vapor in the flue gas 27 is condensed into water, mixed together in the thermal heat storage fluid 31, and discharged from the bottom of the direct heat treatment waste heat recovery tower 29, through the heat storage fluid pump 32 is sent to the heat storage fluid sinking tank 33 for sedimentation, and the dust and water 34 containing HCl and HF are separated and discharged from the bottom of the heat storage fluid sinking tank 33, and the heat storage fluid 31 after dust removal and water removal is
  • the heat storage fluid external circulation pump 35 is sent to the heat storage fluid cooler 37 to be cooled by the cooling water 41 to a normal temperature, and is converted into a cold heat storage fluid 38 and then enters the direct heat treatment waste heat recovery tower 29 for repeated heat absorption.
  • the cooling water 41 absorb
  • the absorption tower 3 has a specification of ⁇ 219 ⁇ 4, a total height of 7.2 meters, 4 layers of packing, 1 meter high per layer, and material 316L stainless steel;
  • the lean liquid tank 11 has a specification of ⁇ 450 ⁇ 3, a total height of 2.0 meters, and a material of 316L stainless steel;
  • the size of the regeneration tower 20 is ⁇ 219 ⁇ 4, the total height is 5.57 meters, the upper layer is 1.5 meters high, and the lower end is empty tower, the material is 316L stainless steel;
  • the concentrating tower 23 has a specification of ⁇ 159 ⁇ 4 and a total height of 6.2 meters.
  • the upper end is a titanium tube tube condenser, the middle layer is 1.5 meters high, and the lower layer is 2.0 meters high.
  • the material is 316L stainless steel.
  • the booster fan 2 model is 2HB710-AH37, the air supply volume is 318m 3 /hr, the wind pressure is -290 ⁇ 390mbar (-29kPa ⁇ 39kPa), Shanghai Liwei Electromechanical Equipment Co., Ltd.;
  • the internal circulation pump 4 is model IHG20-125, flow rate 4.0m 3 /hr, head 20m, 0.75KW, 3 sets, material 316L stainless steel, Shanghai Changshen Pump Manufacturing Co., Ltd.;
  • the models of rich liquid pump 9, desulfurization pump 10 and lean liquid pump 12 are IHG25-160, flow rate 4.0m 3 /hr, head 32m, 1.5KW, 1 each, material 316L stainless steel, Shanghai Changshen Pump Manufacturing Co., Ltd. ;
  • the model of the distilled water pump 24 is WB50/037D, the flow rate is 1.2m 3 /hr, the lift is 14.5 meters, 0.37KW, one set, the material is 316L stainless steel, Guangdong Yongli Pump Co., Ltd.;
  • Flue gas gas flowmeter model is LZB-50 glass rotor flowmeter, measuring range: 50-250m 3 /hr, Jiangyin Keda Instrument Factory;
  • Desulfurization and denitration solution flowmeter rich liquid pump, lean liquid pump and desulfurization pump outlet liquid flow meter model is LZB-32S glass pipeline flowmeter, measuring range: 0.4-4m 3 /hr, Jiangyin Keda Instrument Factory;
  • the liquid flow meter of the circulating pump outlet in the absorption tower is LZB-25S glass pipeline type flowmeter, the measuring range is 0.36-3.6m 3 /hr, 3 sets, Jiangyin Keda Instrument Factory;
  • the gas components analyzed by the inlet and outlet gases of the absorption tower 3 and the concentration tower 23 are all analyzed online by a continuous flue gas analyzer, wherein the contents of SO 2 , NO and O 2 are analyzed by an ultraviolet light JNYQ-I-41 gas analyzer.
  • the CO 2 content was analyzed by JNYQ-I-41C infrared gas analyzer and produced by Xi'an Juengeng Instrument Co., Ltd.; meanwhile, the chemical analysis method was used to analyze and correct the content of SO 2 , NO and CO 2 in the gas and compare with the instrumental analysis value.
  • the content of SO 2 in the gas is analyzed by iodometric method, the content of CO 2 in the gas is analyzed by the cesium chloride method, and the content of NO in the gas is analyzed by the color reaction method of naphthylethylenediamine hydrochloride.
  • the content of SO 2 , NO and CO 2 in the desulfurization and denitrification lean liquid 7, the desulfurization and denitration rich liquid 8 and the distilled water 26 were analyzed by chemical methods.
  • the content of SO 2 in the solution was analyzed by iodometric method and analyzed by the ruthenium chloride method.
  • the content of CO 2 in the solution was analyzed by the colorimetric method of naphthylethylenediamine hydrochloride to determine the NO content in the solution.
  • Gas is conditioned with air, SO 2 , NO and CO 2 , and the gas composition is shown in the test data sheet.
  • NHD solution (a mixture of polyethylene glycol dimethyl ether having a polymerization degree of 4 to 8);
  • the solution When using 15% Na 2 SO 3 (w) aqueous solution, 20% citric acid monopotassium salt (w) aqueous solution, EG solution, PEG400 solution for desulfurization and denitrification, the solution has strong ability to absorb sulfur dioxide, and the absorption rate is up to More than 90%, but no ability to absorb nitrogen oxides, but after two to five days of continuous operation, the solution gradually loses the ability to absorb sulfur dioxide, the solution gradually changes in properties, when heated to above 120 ° C, the solution is also Can not be regenerated.
  • the solution has strong ability to absorb sulfur dioxide, the absorption rate is over 90%, and the ability to absorb nitrogen oxides is also about 50%.
  • the solution gradually turns brownish black, and the ability to absorb sulfur dioxide and nitrogen oxides is reduced to 50% and 20%, respectively, and the solution gradually changes in properties and produces viscosity. Black gelatinous substance.
  • sulfoxide and/or sulfone group-containing additives such as DMSO and/or sulfolane, or their hydroxyl and/or carboxyl substituents
  • these solutions greatly increases the ability of the solution to absorb nitrogen oxides.
  • the use of these solutions can be used in the process and apparatus of the present invention for large scale industrialization for the desulfurization and denitration of flue gases and/or exhaust gases.

Abstract

本发明公开了一种烟道气脱硫脱硝工艺及设备，用脱硫脱硝溶液在吸收塔中吸收烟道气或各种燃烧尾(废)气中的二氧化硫和/或氮氧化物，吸收了二氧化硫和/或氮氧化物的脱硫脱硝溶液在再生塔中用加热和/或气提和/或真空再生释放出二氧化硫和/或氮氧化物，释放出来的二氧化硫和/或氮氧化物又经提浓塔浓缩成较高纯度的二氧化硫和/或氮氧化物产品，再生后的脱硫脱硝溶液循环使用。该工艺及设备具有广泛的工业用途，可用于烟道气、焚烧气、焦炉气、染料厂合成废气、化纤厂排污气，以及含SOx的其它工业原料气或废气的脱硫和/或脱硝。

Description

一种烟道气脱硫脱硝工艺及设备 技术领域
本发明涉及气体脱硫脱硝工业领域，具体涉及一种烟道气或各种燃烧尾(废)气脱硫脱硝的工艺和设备。
背景技术
化石燃料燃烧产生大量的烟道气排放到大气中，其中除含有二氧化硫、三氧化硫、氯化氢、氟化氢、氮氧化物和少量有害有机物外，还含有大量灰尘，这些灰尘中的微小的亲水性和非亲水性粒子(主要为钙盐粒子、铝盐粒子、镁盐粒子、钛盐粒子、铁盐粒子、铅盐粒子、锌盐粒子、钴盐粒子、稀土元素粒子、放射性元素粒子和其它有害元素粒子，以及二氧化硅粒子、莫来石粒子、硅酸盐粒子、磷酸盐粒子等矿物粒子)；这些粒子和烟道气一起被排放至大气中，同时这些粒子表面很容易吸附二氧化硫、三氧化硫、氯化氢、氟化氢、氮氧化物、有害有机物和细菌等，引起大气悬浮粒子(这就是通常所说的PM100、PM10、PM2.5等)含量的显著增加，而引起雾霾和大气光化学反应现象，造成严重的环境污染。
现在烟道气脱硫和脱硝过程是相互独立的，通常是先脱硝然后再脱硫。
现脱硫工艺主要有炉膛喷钙燃烧法脱硫工艺，烟道气、含硫工业原料气和其它废气的干法脱硫工艺和湿法脱硫工艺等。
炉膛喷钙燃烧法脱硫工艺是在燃烧过程中脱硫的一种工艺，是向锅炉炉膛内直接喷入含钙或镁元素的氧化物或碳酸盐等进行固硫的一种方法，或将含钙或镁元素的氧化物或碳酸盐等直接与燃煤混合均匀送入炉膛内燃烧进行固硫的方法；这些含钙或镁元素的氧化物或碳酸盐与燃烧生成的二氧化硫或三氧化硫在高温下反应生产硫酸钙或硫酸镁，同时还会生产亚硫酸钙或亚硫酸镁，这些亚硫酸盐被烟气中的氧气部分氧化成硫酸钙或硫酸镁，达到将部分硫固定在燃烧灰渣中，从而实现脱硫作用。其脱硫效率不高，通常低于80％；且Ca/S(Mg/S)比远大于1.5，含钙或镁元素的氧化物或碳酸盐的资源消耗很大。
干法脱硫工艺是烟道气放空之前经过干法脱硫器，经过脱硫以后再放空。干法脱硫器中装填了固体颗粒干法脱硫剂，干法脱硫剂通常有氧化铁、氧化锌、氧化锰、氧化钴、氧化铬和氧化钼等，这些干法脱硫剂吸收烟道气中的二氧化硫后生成相应的亚硫酸盐，当这些氧化物失去了吸收二氧化硫的能力以后就要重新更换新的干法脱硫剂。干法脱硫剂消耗极大，且 价格昂贵，同时产生大量的废渣需要堆积填埋，会造成严重的污染转移和二次污染现象。
湿法脱硫工艺具体有石灰石湿法脱硫工艺、石灰湿法脱硫工艺、氨法脱硫工艺、双碱法脱硫工艺、磷铵肥脱硫工艺、湿式镁法脱硫工艺、海水法脱硫工艺、韦尔曼-洛德(Wellman-Lord)法脱硫工艺、亚硫酸钠(或钾)法脱硫工艺和有机酸-有机酸盐缓冲溶液法脱硫工艺等。
石灰石湿法脱硫工艺是矿山来的碳酸钙石块经破碎机破碎，再经球磨机磨成目数大于325目的细小粉末，然后将其配制成含碳酸钙粉末10％～15％的浆液；该碳酸钙浆液在脱硫塔中与烟道气逆流接触(也可以顺流接触，或逆流和顺流混合接触)，气体中二氧化硫和浆液中的碳酸钙反应生成亚硫酸钙；碳酸钙浆液转变成亚硫酸钙浆液，亚硫酸钙浆液在脱硫塔的空气强制氧化层被氧化成硫酸钙，亚硫酸钙浆液转变成硫酸钙浆液；硫酸钙浆液流出脱硫塔，进入分离器分离出浆液中的硫酸钙；分离出的水返回用于制备碳酸钙浆液，循环使用；分离出的硫酸钙要么作为废渣填埋或修路基，要么再经纯化后用于制造石膏板。但是本工艺产生很多的硫酸钙固体物，其中还含有部分亚硫酸钙和未反应的碳酸钙等固体废物，石灰石消耗量很大，破碎和磨粉设备庞大，电耗高，投资大，并且在吸收过程中就有固体沉淀物产生，易引起设备堵塞，污水排放量较多，二次污染较严重。同时，由于碳酸钙浆液中含有微小的亲水性和非亲水性粒子(主要为钙盐粒子、铝盐粒子、镁盐粒子、钛盐粒子、铁盐粒子、铅盐粒子、锌盐粒子、钴盐粒子、稀土元素粒子、放射性元素粒子和其它有害元素粒子，以及二氧化硅粒子、莫来石粒子、硅酸盐粒子、磷酸盐粒子等矿物粒子)被烟道气带出，并排放至大气中，同时这些粒子表面很容易吸附二氧化硫、三氧化硫、氯化氢、氟化氢、氮氧化物、有害有机物和细菌等，引起大气悬浮粒子(这就是通常所说的PM100、PM10、PM2.5等)含量的显著增加，而引起雾霾和大气光化学反应现象，造成严重的环境污染。
石灰湿法脱硫工艺是利用锻烧好的氧化钙与水反应生成氢氧化钙水乳浆液，将其配制成含氢氧化钙10％～15％的浆液；氢氧化钙浆液在脱硫塔中与烟道气逆流接触(也可以顺流接触，或逆流和顺流混合接触)，气体中二氧化硫和浆液中的氢氧化钙反应生成亚硫酸钙，氢氧化钙浆液转变成亚硫酸钙浆液；亚硫酸钙浆液在脱硫塔的空气强制氧化层被氧化成硫酸钙，亚硫酸钙浆液转变成硫酸钙浆液；硫酸钙浆液流出脱硫塔，进入分离器分离出浆液中的硫酸钙；分离出的水返回用于制备氢氧化钙浆液，循环使用；分离出的硫酸钙要么作为废渣填埋或修路基，要么再经纯化后用于制造石膏板。本工艺产生很多的硫酸钙固体物，其中还含有部分亚硫酸钙、碳酸钙和未反应的氢氧化钙等固体废物，石灰消耗量很大，设备庞大，投资大， 并且在吸收过程中就有固体沉淀物产生，易引起设备堵塞，污水排放量较多，二次污染较严重；而且，在生产氧化钙的煅烧过程中，要消耗大量的煤，还会产生严重的污染。同时，由于氢氧化钙浆液中含有微小的亲水性和非亲水性粒子(主要为钙盐粒子、铝盐粒子、镁盐粒子、钛盐粒子、铁盐粒子、铅盐粒子、锌盐粒子、钴盐粒子、稀土元素粒子、放射性元素粒子和其它有害元素粒子，以及二氧化硅粒子、莫来石粒子、硅酸盐粒子、磷酸盐粒子等矿物粒子)被烟道气带出，并排放至大气中，同时这些粒子表面很容易吸附二氧化硫、三氧化硫、氯化氢、氟化氢、氮氧化物、有害有机物和细菌等，引起大气悬浮粒子(这就是通常所说的PM100、PM10、PM2.5等)含量的显著增加，而引起雾霾和大气光化学反应现象，造成严重的环境污染。
氨法脱硫工艺是用一定浓度的氨水作吸收剂，将烟道气中的二氧化硫吸收，反应生成亚硫酸氢铵，再经强制氧化成硫酸氢铵，硫酸氢铵最后经氨碱化成硫酸铵，分离硫酸铵作为化肥副产物。其工艺是经除尘和气气换热器换热以后的烟道气在脱硫塔中与氨水逆流或顺流或逆流和顺流的混合流动的形式接触，烟道气中的二氧化硫被氨水吸收转变成亚硫酸氢铵；脱硫后的烟道气经过气气换热器换热以后，经烟囱排入大气；经过脱硫以后生产的亚硫酸氢铵溶液经脱硫塔中的强制氧化段或单独的强制氧化器被空气或臭氧氧化后转变成硫酸氢铵，然后再进入碱化器用氨气或浓氨水碱化转变成硫酸铵，并经结晶器结晶，分离、干燥，得硫酸铵肥料副产品；分离出的氨水母液继续配入氨，增加氨的浓度后继续回收利用。氨法脱硫工艺脱硫效率高、溶液循环量小；但是，氨毒性大、挥发性极强、沸点低，烟气中夹带氨的现象严重，造成大量的氨损失，造成大气氨二次污染现象，同时，氨法脱硫工艺氨消耗量很大，氨转化成了低价值的硫酸铵，脱硫成本高，还易产生结晶堵塞设备和管道；而且氨的腐蚀性大，设备腐蚀严重，且氨的生产过程是高能耗、高污染的过程，过度消耗氨实际也是间接增大环境污染和增加能耗的过程，所以应尽量减少氨的使用。
双碱法脱硫工艺是用NaOH、或Na2CO3、或Na2SO3等水溶性强的碱性金属盐类物质的水溶液，在脱硫塔中吸收烟道气中的二氧化硫，反应生成水溶性的亚硫酸氢钠或碱性金属的亚硫酸氢盐；净化后的烟道气经烟囱排入大气；亚硫酸氢钠或碱性金属的亚硫酸氢盐水溶液送至石灰反应器中用CaO或CaCO3进行中和反应，在反应过程中同时用空气进行氧化，生成硫酸钙沉淀，分离得石膏；溶液又转化成NaOH、或Na2CO3等水溶性强的碱性金属盐类物质的水溶液，重复使用。双碱法脱硫工艺是为了避免纯石灰石(或石灰)法工艺的沉淀堵塞问题，但实质还是用石灰石(或石灰)作为脱硫剂。
磷铵肥脱硫工艺(PAFP)是利用天然磷矿石和氨为原料，在烟气脱硫过程中直接生产磷铵复合肥料的一种脱硫技术和工艺。该工艺主要由吸附、萃取、中和、吸收、氧化、浓缩干燥等单元操作组成。吸附是利用活性炭作为第一级脱硫吸附介质，对烟气中的SO2进行吸附处理，在有氧气条件下，SO2被催化氧化成SO3，活性炭的吸附容量接近饱和时，对活性炭洗涤再生即能得到稀硫酸，其浓度大于30％，再生后的活性炭重复使用；萃取磷矿石制磷酸是将一级脱硫制备的稀硫酸与磷矿(Ca10(PO4)F2)粉发生反应，生成氟化氢、磷酸和硫酸钙；萃取过滤后可获得磷酸，磷矿萃取率大于90％，稀磷酸浓度大于10～14％；中和是将氨与萃取获得的磷酸反应制备磷酸氢二铵，磷酸氢二铵作为二级脱硫剂，磷酸氢二铵在第二级脱硫塔中吸收SO2生成亚硫酸氢二铵和磷酸二氢铵；氧化是将溶液中的亚硫酸氢二铵氧化成硫酸铵，氧化后的溶液经浓缩、干燥的固体磷酸二氢铵和硫酸铵复合肥料。该工艺非常复杂，投资大，蒸汽消耗量大，能耗高；同时，需要消耗大量的天然磷矿石，所以该技术和工艺不是任何地方都适用，只有有天然磷矿石的地方才可以使用。
湿式镁法脱硫工艺是氧化镁或氢氧化镁的浆液在脱硫塔中与烟道气逆流接触(也可以顺流接触，或逆流和顺流混合接触)，气体中二氧化硫和浆液中的氧化镁或氢氧化镁反应生成亚硫酸镁；氧化镁或氢氧化镁浆液转变成亚硫酸镁浆液，亚硫酸镁浆液经沉淀，进入分离器分离出浆液中的亚硫酸镁；分离出的水返回用于制备氧化镁或氢氧化镁浆液，循环使用；分离出的亚硫酸镁在1235K以上煅烧，生产氧化镁和气体二氧化硫，生产的氧化镁重复使用，二氧化硫可以回收。但是本工艺生成的亚硫酸镁固体物容易堵塞管道和设备，同时，亚硫酸镁要在1235K以上煅烧才能分解，能耗高，投资大，二次污染较严重。同时，由于氧化镁或氢氧化镁浆液中含有微小的亲水性和非亲水性粒子(主要为钙盐粒子、铝盐粒子、镁盐粒子、钛盐粒子、铁盐粒子、铅盐粒子、锌盐粒子、钴盐粒子、稀土元素粒子、放射性元素粒子和其它有害元素粒子，以及二氧化硅粒子、莫来石粒子、硅酸盐粒子、磷酸盐粒子等矿物粒子)被烟道气带出，并排放至大气中，同时这些粒子表面很容易吸附二氧化硫、三氧化硫、氯化氢、氟化氢、氮氧化物、有害有机物和细菌等，引起大气悬浮粒子(这就是通常所说的PM100、PM10、PM2.5等)含量的显著增加，而引起雾霾和大气光化学反应现象，造成严重的环境污染。
海水法脱硫工艺是利用海水中含有大量的钙、镁、铝、钠、钾等离子的盐，尤其是碳酸盐，具有较高的碱度。这种用海水直接吸收烟道气中二氧化硫的方法，就是海水脱硫法。其工艺非常简单，在脱硫塔中，海水和烟道气直接接触，吸收烟气中的二氧化硫，海水中的碱 性物质(尤其是碳酸盐；为了增大海水的碱性，有时人为地向海水中加入氧化钙或氢氧化钙)和二氧化硫反应生产亚硫酸盐；吸收了二氧化硫的海水经暴晒和氧化后，其中的亚硫酸盐被氧化成硫酸盐，然后直接排入大海。该技术和工艺只能在海边适用，因为海水消耗量特大。由于大量的硫酸盐排入大海，或多或少会对海水环境造成破坏。
亚硫酸钠(或钾)法脱硫工艺和湿式镁法脱硫工艺相似，是以亚硫酸钠(或钾)的水溶液在脱硫塔中与烟道气逆流接触(也可以顺流接触，或逆流和顺流混合接触)，气体中二氧化硫和溶液中的亚硫酸钠(或钾)反应生成亚硫酸氢钠(或钾)；亚硫酸钠(或钾)溶液转变成亚硫酸氢钠(或钾)溶液，亚硫酸氢钠(或钾)溶液进入蒸汽加热再生器中再生，亚硫酸氢钠(或钾)溶液转变成亚硫酸钠(或钾)水溶液，同时释放出二氧化硫；亚硫酸钠(或钾)水溶液循环使用，二氧化硫气体可以回收作为副产品。该工艺构思比较好，但是实际试验表明亚硫酸氢钠(或钾)溶液在蒸汽加热时再生率非常低，只有极少部分亚硫酸氢钠(或钾)能转变成亚硫酸钠(或钾)，绝大多数亚硫酸氢钠(或钾)无法分解，且蒸汽消耗量很大。所以本工艺一直无法实现工业化。
韦尔曼-洛德(Wellman-Lord)法脱硫工艺实际上就是改进的亚硫酸钠循环法工艺，只是在亚硫酸钠循环法工艺中增加了多效蒸发工序，用于蒸发脱硫液使亚硫酸钠结晶出来。该方法在美国、德国、法国和日本有大规模应用实例，但其蒸汽消耗很大，能耗高。
有机酸-有机酸盐缓冲溶液法脱硫工艺是用有机酸和有机酸盐组成的缓冲溶液作为脱硫液，在脱硫塔中与烟道气逆流接触(也可以顺流接触，或逆流和顺流混合接触)，气体中二氧化硫和溶液中的有机酸盐反应生成亚硫酸氢盐和有机酸；该溶液进入蒸汽加热再生器中再生，溶液中的亚硫酸盐转变成有机酸盐，溶液仍然转变成有机酸-有机酸盐缓冲溶液，重复使用，同时释放出二氧化硫，二氧化硫气体可以回收作为副产品。该工艺构思比较好，但是实际试验表明在有机酸-有机酸盐缓冲溶液中亚硫酸盐在蒸汽加热时再生率非常低，只有极少部分亚硫酸盐能转变成有机酸盐，绝大多数亚硫酸盐无法分解，且蒸汽消耗量很大，所以本工艺一直无法实现工业化。在该工艺的基础上，有人向有机酸-有机酸盐缓冲溶液中加入氧化钙(或氢氧化钙)使没有再生的亚硫酸钠转化成亚硫酸钙，沉淀分离，溶液再生彻底，再生后的有机酸-有机酸盐缓冲溶液循环使用，但实际该工艺中的脱硫剂还是氧化钙(或氢氧化钙)。由于溶液中含有一些钙离子，在脱硫过程中会产生沉淀，堵塞管道和设备。
现在实际生产中所用的脱硝工艺是催化氨脱硝工艺。
催化氨脱硝工艺是温度约在150℃～500℃和在催化剂作用的条件下，将氨直接喷入烟道 气中，在催化剂层内，氨气和NOX反应生成N2和H2O达到消除NOX的目的。该工艺氨消耗量较大，由于烟道气中含有约4％～9％的O2，氨气和O2会反应生成NOX而消耗氨，同时氨反应不彻底，有部分氨和烟道气一同排入大气，增加氨的损失，产生二次污染现象。氨的生产过程中要消耗大量的化石燃料，产生大量的废气、废渣和废水，是一个严重的环境污染过程，因此应尽量避免氨的使用。
发明内容
为了使我们的专利技术“聚乙二醇脱除气体中SOx的方法”、(专利号ZL 2009100090 58.1)“乙二醇脱除烟道气中SOx的方法”(专利号：ZL200710110446.X)、“改性聚乙二醇脱除气体中SOx的方法”(申请号201310409296.8)、“复合醇胺类溶液脱除气体中SOx的方法”(申请号：201310481557.7)、“乙二醇类复合溶液脱除气体中SOx的方法”(申请号：201310682799.2)和“多元醇复合溶液脱除气体中SOx的方法”(申请号：201310682382.6)等更好地实现大规模的工业化应用，我们发明了与这些专利技术(以下称为“我们的专利技术”)相适应的一种烟道气脱硫脱硝工艺及设备。
在本发明中，所述烟道气脱硫脱硝工艺及设备中所用的脱硫脱硝溶液是含多醇类(和/或含聚多醇类)的复合溶液；这些脱硫脱硝溶液的组成、含量和特征在我们的专利技术中都已经叙述了，这里就不再赘述。为了使脱硫脱硝溶液具有强大的吸硫和脱硝能力和解析能力，可以向所述含多醇类(和/或含聚多醇类)的脱硫脱硝溶液中加入适当的添加剂；向脱硫脱硝溶液中加入什么添加剂，及添加剂的组成、含量和特征也已经在我们的专利技术中叙述了，这里就不再赘述。
本发明的烟道气脱硫脱硝工艺及设备具有同时脱硫和脱硝的作用，其脱硫的原理在我们的专利技术中都已经叙述了，这里就不再赘述；这里仅叙述其脱硝原理如下：
脱硝主要是脱除烟道气中的氮氧化物NOX(x指氧原子的数目)(氮氧化物包括NO2、NO、N2O等，烟道气中90％以上是NO)。脱硫脱硝溶液的组成为EG(乙二醇)和/或PEG(聚乙二醇)、水、多羧酸类和/或多羧酸盐和添加剂组成。
为了更清晰的叙述本发明的基本原理，下面仅以乙二醇、柠檬酸及其盐和含砜类基团的物质为例说明本发明的脱硫脱销溶液的酯化机制和脱硝机制，但并不是限定本发明的脱硫脱硝溶液仅仅是由乙二醇、柠檬酸及其盐类和含砜和/或亚砜类基团的物质所组成，而是由乙二醇和/或聚乙二醇、有机酸和/或有机酸盐和添加剂(在我们的专利技术中已经列举了，这里就 不再列举)组成的脱硫脱销溶液。
Figure PCTCN2015080761-appb-000001
当脱硫脱销溶液在吸收塔中和烟道气接触时，会发生如下脱硝反应：
Figure PCTCN2015080761-appb-000002
吸收了NOX的脱硫脱硝溶液，在再生塔中会发生如下解析反应：
Figure PCTCN2015080761-appb-000003
Figure PCTCN2015080761-appb-000004
经过再生以后的脱硫脱硝溶液循环使用。
采用我们前期提出专利申请的“改性聚乙二醇脱除气体中SOx的方法”(申请号201310409296.8)、“复合醇胺类溶液脱除气体中SOx的方法”(申请号：201310481557.7)、“乙二醇类复合溶液脱除气体中SOx的方法”(申请号：201310682799.2)和“多元醇复合溶液脱除气体中SOx的方法”(申请号：201310682382.6)等技术所指导的脱硫溶液不仅具有脱除气体中二氧化硫的能力，还具有吸收气体中氮氧化物的能力。尤其，向这些溶液中添加少量的含亚砜和/或砜基团的添加剂(如DMSO和/或环丁砜，或它们的羟基和/或羧基取代物)时，溶液吸收氮氧化物的能力大幅提高。
本发明的烟道气脱硫脱硝工艺包括：余热回收、脱硫脱硝、脱硫脱硝溶液再生和二氧化硫及NOX提浓的关键过程。
1)余热回收过程：采用换热回收方式将烟道气的温度降至50℃以下，并进行余热回收。
由于现在烟道气通常排烟的温度为130℃至170℃，且排烟量巨大，含有相当大的显热和潜热(烟道气中水蒸气所含热量)。我们把这种将烟道气从130℃至170℃降至50℃以下，并设法回收这部分热量的过程称为余热回收过程。余热回收的方式通常有间接换热回收、直接换热回收、间接换热和直接换热同时回收的方式。间接换热回收方式是在壁管式换热器中，热的烟道气走换热壁一边，蓄热流体走壁的另一边，烟道气与蓄热流体互不接触，蓄热流体通过壁面导热间接式将烟道气的温度冷却，同时蓄热流体温度升高；直接换热方式是在直接换热器中，蓄热流体和烟道气直接接触(既可以是逆流接触，也可以是顺流接触)，将烟道气的温度冷却，同时蓄热流体温度升高；间接换热和直接换热同时回收的方式是在余热回收的过程中，既有直接换热回收方式，又有间接换热回收的方式。在直接换热回收的方式中，这里所述的蓄热流体是液体，最好是高沸点、不易挥发、与水不相溶的液体，如硅油、石钠油、高沸点脂肪油等；在间接换热回收的方式中，这里所述的蓄热流体既可以是液体，也可以是气体。吸收了烟道气中热量的高温蓄热流体可以作为热源，用于锅炉补充水的加热，也可以用于其它任何需要加热的地方进行加热。考虑到间接换热回收装置的高成本，优选采用直接换热回收方式、间接换热和直接换热同时回收的方式进行余热回收。
2)脱硫脱硝过程：在吸收塔中通过脱硫脱硝溶液吸收烟道气或各种燃烧尾(废)气中的二氧化硫和/或氮氧化物，所述脱硫脱硝溶液为含多醇类和/或含聚多醇类的复合溶液。
温度低于50℃的烟道气，在吸收塔中，与脱硫脱硝溶液(通常称为“脱硫脱硝贫液”)直接接触，烟道气中的二氧化硫被脱硫脱硝贫液吸收，同时，烟道气中的氮氧化物和二氧化碳也会部分被脱硫脱硝贫液吸收，然后脱硫脱硝贫液转变成“脱硫脱硝富液”，脱硫脱硝富液流出吸收塔，并送去脱硫脱硝溶液再生过程。经脱硫脱硝净化后的烟道气(其温度比环境温度高5℃比较好)通过烟囱排入大气。在脱硫脱硝过程中的脱硫脱硝溶液吸收二氧化硫的原理在我们的专利技术中已经作了相当详细的叙述，这里就不再叙述。
3)脱硫脱硝溶液再生过程：吸收了二氧化硫和/或氮氧化物的脱硫脱硝富液在再生塔中通过加热和/或气提和/或真空再生方式释放出二氧化硫和/或氮氧化物，再生后的脱硫脱硝溶液循环使用。
脱硫脱硝过程送来的脱硫脱硝富液温度较低，经过与从再生塔的底部流出的脱硫脱硝贫液进行间接式热交换(通常是通过列管式换热器进行)后，再被加热至90℃以上，然后从再生塔的上端进入，在再生塔中脱硫脱硝富液与底部来的气提用的热气体(气提用的气体可以是氮气、氩气或水蒸汽等惰性气体，温度大于再生塔中压力时所对应的水的饱和蒸汽温度)充分逆流接触，溶解在脱硫脱硝富液中的二氧化硫、氮氧化物和二氧化碳等解析出来，并和气提用气体混合形成混合气体，该混合气体从再生塔的顶部出来，并送去提浓过程进行提浓处理；再生后的脱硫脱硝富液变成脱硫脱硝贫液，从再生塔的底部流出，经热交换和冷却至50℃以下后送至脱硫脱硝过程循环利用。这里使用了加热和气提方式来对脱硫脱硝溶液进行再生，所以称为气提和加热脱硫脱硝溶液再生塔(或脱硫脱硝溶液再生器)，是二元再生器。为了提高再生效果，采用真空泵抽真空的方式，使脱硫脱硝溶液再生塔中具有一定的真空度，同时使用了气提、加热和真空三种方式来对脱硫脱硝溶液进行再生，因此称为气提、加热和真空脱硫脱硝溶液再生塔(或脱硫脱硝溶液再生器)，是三元再生器。依次类推，为了进一步提高再生效果，在脱硫脱硝溶液再生塔(或脱硫脱硝溶液再生器)中还可以安装超波再生系统和/或微波再生系统和/或辐射再生系统，组成气提、加热、真空和超波和/或微波和/或辐射等多元脱硫脱硝溶液再生塔(或脱硫脱硝溶液器)，是多元再生器。
4)二氧化硫和/或氮氧化物提浓过程：释放出来的二氧化硫和/或氮氧化物经提浓塔浓缩成较高纯度的二氧化硫气体(或液体)产品和/或氮氧化物气体产品。
脱硫脱硝溶液再生过程释放出来的混合气体从提浓塔的中段进入，和提浓塔顶部冷凝下 来的水逆流接触将混合气体中的水蒸汽冷凝下来，除去水蒸汽的混合气体从提浓塔顶部流出，该气体中主要含二氧化硫成分，同时还含有部分氮氧化物和二氧化碳等成分，其中二氧化硫可以进一步压缩、冷却加工成纯液体二氧化硫、或用焦炭还原成硫磺、或加工成硫酸，氮氧化物可以用于还原成氮气、或作为硝酸的原料，剩余的气体可以返回去脱硫脱硝过程处理以后放空；水蒸汽从提浓塔底端进入，和冷凝下来的水逆流接触，水蒸汽将冷凝水中的残余二氧化硫、氮氧化物等有害成分提出来，以达到提浓二氧化硫、氮氧化物气体浓度作用，同时，去除冷凝水中的有害二氧化硫和氮氧化物等成分，使冷凝水变成蒸馏水，从提浓塔底部流出，并回收至锅炉用水。
本发明的烟道气脱硫脱硝工艺及设备中对应的关键设备有：余热回收塔(或余热回收器)、吸收塔、再生塔和提浓塔，其中：
余热回收塔：用于使烟道气与蓄热流体进行换热，将烟道气的温度降至50℃以下，并进行余热回收；
吸收塔：用于使降温后的烟道气与脱硫脱硝溶液直接接触，脱硫脱硝溶液吸收烟道气中的二氧化硫和/或氮氧化物成为脱硫脱硝富液，然后从吸收塔排出；所述脱硫脱硝溶液为含多醇类和/或聚多醇类的复合溶液；
再生塔：用于使脱硫脱硝富液通过加热和/或气提和/或真空再生方式解析出二氧化硫和/或氮氧化物成为脱硫脱硝贫液，再生得到的脱硫脱硝贫液又送回吸收塔循环利用；
提浓塔：用于将脱硫脱硝富液在再生塔中再生释放出来的包含二氧化硫和/或氮氧化物的混合气体中的水蒸汽通过冷凝去除，二氧化硫和/或氮氧化物则浓缩成较高纯度的二氧化硫和/或氮氧化物气体或液体产品。
进一步的，所述余热回收塔可以设置有一级或多级余热回收内循环泵，以增加蓄热流体循环量；所述吸收塔也可以设置有一级或多级脱硫脱硝内循环泵，以增加脱硫脱硝溶液循环量。
优选的，在所述吸收塔与再生塔之间设置热交换器，来自吸收塔的脱硫脱硝富液与从再生塔流出的脱硫脱硝贫液通过该热交换器进行间接式热交换。
在本发明的一个具体实施方式中，所述烟道气脱硫脱硝工艺及设备中的脱硫脱硝、脱硫脱硝溶液再生和二氧化硫和/或氮氧化物提浓工艺流程和设备见图1所示。
本发明的烟道气脱硫脱硝工艺及设备中的余热回收流程和设备优选的有二种，分别见图2和图3所示。
本发明与传统的湿法脱硫工艺(如钙法脱硫工艺、氨法脱硫工艺等)相比，具有如下优点：①传统的湿法脱硫工艺用于烟道气脱硫时，其副产物是硫酸钙和亚硫酸钙，或硫酸铵和亚硫酸铵，本发明的烟道气脱硫脱硝工艺及设备的副产物是高纯度的二氧化硫，这些副产物是重要的化工原材料，具有广泛的市场和重要的应用价值；②传统的湿法脱硫工艺(如钙法脱硫工艺、氨法脱硫工艺等)所用的脱硫剂是碳酸钙、氧化钙和/或氨；用碳酸钙作脱硫剂时，需要消耗大量的碳酸钙，开采碳酸钙会严重破坏环境，造成水土流失，山体滑坡和生态环境的破坏；用氧化钙作脱硫剂时，需要消耗大量的氧化钙，氧化钙是由碳酸钙和煤煅烧而获得，也要大量开采碳酸钙，并消耗大量煤，会造成严重二次污染，造成水土流失，山体滑坡和生态环境的破坏；用氨作脱硫剂时，本身氨的生产过程是严重的高污染和高能耗、易燃和易爆的过程，同时由于氨易挥发，会被烟道气大量带入环境造成严重二次污染现象；本发明的烟道气脱硫脱硝工艺及设备所对应的脱硫脱硝剂是高沸点、无毒、无害的安全性很高的有机多醇多酸酯类溶剂，全循环使用，不需要消耗碳酸钙和/或氧化钙和/或氨，无任何二次污染现象；③传统的湿法脱硫工艺(如钙法脱硫工艺)由于使用大量矿物质碳酸钙或氧化钙，其浆液中含有微小的亲水性和非亲水性粒子(主要为钙盐粒子、铝盐粒子、镁盐粒子、钛盐粒子、铁盐粒子、铅盐粒子、锌盐粒子、钴盐粒子、稀土元素粒子、放射性元素粒子和其它有害元素粒子，二氧化硅粒子、莫来石粒子、硅酸盐粒子、磷酸盐粒子等矿物粒子)被烟道气一起排放至大气中，同时这些粒子表面很容易吸附二氧化硫、三氧化硫、氯化氢、氟化氢、氮氧化物、有害有机物和细菌等，引起大气悬浮粒子(这就是通常所说的PM100、PM10、PM2.5等)含量的显著增加，而引起雾霾和大气光化学反应现象，造成严重的环境污染；本发明的烟道气脱硫脱硝工艺及设备用于烟道气或废气脱硫脱硝是没有这些现象，如本发明得到广泛应用可以消除雾霾和大气光化学反应现象；④传统的湿法脱硫工艺运行费用高，且无法产生经济效益，本发明的烟道气脱硫脱硝工艺及设备运行费用低，脱硫脱硝效率高，同时将废物转变成宝贵的化工原料，可以产生较大的经济效益、社会效益和环境效益；⑤传统的湿法脱硫工艺在整个脱硫和再生过程中会产生不溶性钙盐或铵盐沉淀，引起设备和管道堵塞，本发明的烟道气脱硫脱硝工艺及设备不会产生不溶性钙盐或铵盐沉淀；⑥传统的湿法脱硫工艺只适用于较低硫含量气体脱硫，本发明的烟道气脱硫脱硝工艺及设备既可以用于低硫含量气体脱硫脱硝，也可以用于高硫含量气体脱硫脱硝。同时，本发明的烟道气脱硫脱硝工艺及设备的脱硫脱硝的净化度高，可以将气体中的总硫含量稳定地降至50mg/m3以下，且溶液沸点高，损失少，脱硫脱硝的气液比大，能耗低，同时运行费用低，流程短，投资小，操作简单。
本发明的烟道气脱硫脱硝工艺及设备具有广泛的工业用途，既可以用于同时脱除气体中的二氧化硫和氮氧化物，也可以用于单独脱除气体中的二氧化硫，或单独脱除气体中的氮氧化物，可将其用于烟道气、焚烧气、焦炉气、染料厂合成废气、化纤厂排污气，以及含SOx的其它工业原料气或废气的脱硫脱硝，上述含硫气体中的总含硫量均小于99.9％(体积比)。
附图说明
图1是烟道气脱硫脱硝、脱硫脱硝溶液再生和二氧化硫和/或氮氧化物提浓工艺流程和设备的示意图。
图1中：1是温度低于50℃的烟道气，2是增压风机，3是吸收塔，4是脱硫脱硝内循环泵，5是烟囱，6是脱硫脱硝后的烟道气，7是脱硫脱硝贫液，8是脱硫脱硝富液，9是富液泵，10是脱硫脱硝泵，11是贫液槽，12是贫液泵，13是冷却器，14是热交换器，15是冷却水，16是热水，17是富液加热器，18是热介质，19是冷介质，20是再生塔，21是再生解析气，22是气提用蒸汽，23是提浓塔，24是蒸馏水泵，25是浓缩的二氧化硫和/或氮氧化物气体，26是蒸馏水。图中用圆圈圈起来的各符号所代表的意义：F1、F2、F3、F4分别表示烟道气1的流量、脱硫贫液7的流量、进再生塔20的蒸汽流量、进提浓塔23的蒸汽流量；A1为烟道气1的组成、A2为脱硫脱硝后的烟道气6的组成、A3为浓缩的二氧化硫和/或氮氧化物气体25的组成、A4为脱硫脱硝富液8中的SO2和NO含量、A5为再生后脱硫脱硝贫液7中的SO2和NO的含量、A6为蒸馏水26中的SO2和NO含量；P1为吸收塔3底部压力、P2为吸收塔3顶部压力、P3为再生塔20中压力、P4为蒸汽22的压力、P5为提浓塔23中的压力；T1为烟道气1的温度、T2为脱硫脱硝后的烟道气6的温度、T3为吸收塔3中温度、T4为进吸收塔3的脱硫脱硝贫液7的温度、T5为出冷却器13的脱硫脱硝贫液7的温度、T6为出热交换器14脱硫脱硝贫液的温度、T7为进热交换器14脱硫脱硝富液的温度、T8为进热交换器14脱硫脱硝贫液的温度、T9为出热交换器14脱硫脱硝富液的温度、T10为脱硫脱硝富液进再生塔20的温度、T11为再生塔20中的温度、T12为再生解析气21的温度、T13为蒸汽22的温度、T14为蒸馏水26的温度、T15为提浓塔23中的温度、T16为浓缩的二氧化硫和/或氮氧化物气体25的温度。
图2是烟道气余热回收的直接换热回收方式的工艺流程和设备示意图。
图2中：27是来自锅炉的温度为130～180℃的烟道气，28是余热回收后温度低于50℃的烟道气，29是直接换热余热回收塔，30是余热回收内循环泵，31是热蓄热流体，32是蓄热 流体泵，33是蓄热流体沉清槽，34是灰尘和水，35是蓄热流体外循环泵，36是蓄热流体放热器，37是蓄热流体冷却器，38是冷蓄热流体，39是被加热介质，40是被加热后介质，41是冷却水，42是热水。
图3是烟道气余热回收的直接换热和间接换热同时进行的热回收方式的工艺流程和设备示意图。
图3中：27是来自锅炉的温度为130～180℃的烟道气，28是余热回收后的温度低于50℃的烟道气，29是直接换热余热回收塔，30是余热回收内循环泵，31是热蓄热流体，32是蓄热流体泵，33是蓄热流体沉清槽，34是灰尘和水，35是蓄热流体外循环泵，37是蓄热流体冷却器，38是冷蓄热流体，39是被加热介质，40是被加热后介质，41是冷却水，42是热水，43是烟道气间接换热热回收器。
具体实施方式
下面结合具体的实施方案来描述本发明所述的烟道气脱硫脱硝工艺及设备。所述的实施方案是为了更好地说明本发明，而不能理解为是对本发明的权利要求的限制。
其操作方法如下：
烟道气脱硫脱硝、脱硫脱硝溶液再生、二氧化硫和/或氮氧化物提浓工艺流程和设备的操作方式如图1所示：温度低于50℃的烟道气1经增压风机2增压后从底部进入吸收塔3，同时，脱硫脱硝贫液7从顶部进入吸收塔3，在吸收塔3中，烟道气1和脱硫脱硝贫液7直接接触，此时烟道气1中的二氧化硫、部分氮氧化物和二氧化碳被脱硫脱硝贫液7吸收，被吸收了二氧化硫、部分氮氧化物和二氧化碳的烟道气1转变成脱硫脱硝后的烟道气6从吸收塔3顶部流出，再经烟囱5排入大气中，同时在线分析温度低于50℃的烟道气1和脱硫脱硝后的烟道气6中的二氧化硫、氮氧化物和二氧化碳的含量A1和A2。为了增大气液接触面，延长气液接触时间，提高脱硫效率，需要在吸收塔3中增加脱硫脱硝贫液7的循环量，需要增加脱硫脱硝贫液7的循环量就需要在吸收塔3中增加脱硫脱硝内循环泵4的级(或台)数，增加脱硫脱硝内循环泵4的级(或台)数可以是0级、或1级、或2级、或3级、或4级...或n级(n为正整数)等，具体需要增加的级数可以由吸收塔3顶部出口脱硫脱硝后的烟道气6的二氧化硫和/氮氧化物含量来决定；吸收了二氧化硫、部分氮氧化物和二氧化碳的脱硫脱硝贫液7转变成脱硫脱硝富液8，从吸收塔3的底部流出，经富液泵9增压，又经热交换器14的壳程与再生塔20来的热的脱硫脱硝贫液7进行热交换，温度升高，然后再经过富液 加热器17被热介质18(热介质可以是温度大于100℃的液体、也可以是130℃～170℃的烟道气，也可以是温度大于100℃的水蒸汽)加热至90℃以上，温度大于90℃的脱硫脱硝富液8从上端进入再生塔20中，同时气提用蒸汽22从底部进入再生塔20中，在再生塔20中温度大于90℃的脱硫脱硝富液8与气提用蒸汽22进行直接接触，此时脱硫脱硝富液8中的二氧化硫、部分氮氧化物和二氧化碳解析出来，并进入气提用蒸汽22中混合成再生解析气21从再生塔20的顶部流出，释放了二氧化硫、部分氮氧化物和二氧化碳的温度大于90℃的脱硫脱硝富液8转变成温度大于90℃的热的脱硫脱硝贫液7，从再生塔20底部流出，经过热交换器14的管程与壳程中的由富液泵9送来的脱硫脱硝富液8进行热交换，温度降低，降低了温度的脱硫脱硝贫液7走冷却器13的管程，被壳程的冷却水15冷却至常温，并由贫液泵12增压送至贫液槽11中，然后贫液槽11中的脱硫脱硝贫液7由脱硫泵10增压又送至吸收塔3中进行脱硫脱硝作用，脱硫脱硝溶液就是这样由脱硫脱硝贫液7在吸收塔3中吸收二氧化硫、部分氮氧化物和二氧化碳转变成脱硫脱硝富液8，脱硫脱硝富液8在再生塔20中被加热、气提和/或真空再生又转变成脱硫脱硝贫液7，脱硫脱硝贫液7又循环使用，如此连续循环。从再生塔20的顶部流出的再生解析气21从中部进入提浓塔23中，与提浓塔23上端冷凝下来的蒸馏水接触，再生解析气21中的水蒸汽在提浓塔23的冷凝段被冷却水15冷凝下来，不冷凝的二氧化硫、氮氧化物和二氧化碳等混合气体组成的浓缩的二氧化硫和/氮氧化物气体25从提浓塔23流出，可以作为原料气去回收，同时冷凝下来的蒸馏水中含有二氧化硫等物质，继续流到提浓塔23的底部，与底部来的气提用蒸汽22接触，蒸馏水中的二氧化硫等气体被气提用蒸汽22气提解析出来，使冷凝水中基本不含二氧化硫等气体，达到回收用的蒸馏水26标准，用蒸馏水泵24送去回收使用。在整个流程中，冷却水15被加热转变成热水16，可以回收作为锅炉补充热水用；热介质18经过释放热量以后转变成冷介质19；冷介质19可以是蒸馏水或其它液体，它可以继续用去吸收热量，然后转变成热介质18重复使用；当冷介质19是降温后的烟道气时，继续降温至温度低于50℃的烟道气1。
烟道气余热回收的直接换热回收方式的工艺流程和设备的操作方式见图2所示：来自锅炉的温度为130～180℃的烟道气27从底部进入直接换热余热回收塔29中，与塔顶喷淋下来的冷蓄热流体38直接接触，进行直接换热，同时来自锅炉的温度为130～180℃的烟道气27被冷却转变成温度低于50℃的烟道气28从直接换热余热回收塔29的顶部排出。为了增大气液接触面，延长气液接触时间，提高换热效果，需要在直接换热余热回收塔29中增加蓄热流体循环量，需要增加蓄热流体的循环量就需要在直接换热余热回收塔29中增加余热回收内循 环泵30的级(或台)数，增加余热回收内循环泵30的级(或台)数可以是0级、或1级、或2级、或3级、或4级...或n级(n为正整数)等，具体需要增加的级数可以由直接换热余热回收塔29的顶部排出的烟道气28的温度高低来决定。在直接换热余热回收塔29中，冷蓄热流体38吸收烟道气27的热量后转变成热蓄热流体31，其温度接近或低于烟道气27的温度，同时冷蓄热流体38还会将烟道气27中的HCl、HF、微小灰尘(包括水溶性和非水溶性，即极性和非极性微小粒子，也就是通常说的PM100和/或PM50和/或PM2.5等各种粒子)吸附富集，还会将烟道气27中的部分水蒸汽冷凝成水，一同混合在热蓄热流体31中，并从直接换热余热回收塔29的底部排出，经蓄热流体泵32送至蓄热流体沉清槽33中进行沉清，分离出含HCl、HF的灰尘和水34从蓄热流体沉清槽33的底部排出，除尘和除水后的热蓄热流体31由蓄热流体外循环泵35提压送至蓄热流体放热器36中，在蓄热流体放热器36中将大部分热量传给被加热介质39，被加热介质39吸收热量后变成被加热后介质40，并作为热源去回收热量。释放了部分热量的热蓄热流体31又进入蓄热流体冷却器37中被冷却水41冷却至常温，并转变成冷蓄热流体38又进入直接换热余热回收塔29中进行重复吸热，同时，冷却水41吸收热量后转变成热水42，其中的热量可以回收使用。
烟道气余热回收的直接换热和间接换热同时回收方式的工艺流程和设备的操作方式见图3所示：锅炉来温度为130～180℃的烟道气27进入烟道气间接换热热回收器43中，经间接换热的方式，部分热量被被加热介质39吸收转变成被加热后介质40，被加热后介质40的温度接近但低于锅炉来温度为130～180℃的烟道气27的温度，被加热后介质40可以作为热源回收；释放了部分热量的烟道气27从底部进入直接换热余热回收塔29中，与塔顶喷淋下来的冷蓄热流体38直接接触，进行直接换热，同时烟道气27被冷却转变成温度低于50℃的烟道气28从直接换热余热回收塔29的顶部排出，为了增大气液接触面，延长气液接触时间，提高换热效果，需要在直接换热余热回收塔29中增加蓄热流体循环量，需要增加蓄热流体的循环量就需要在直接换热余热回收塔29中增加余热回收内循环泵30的级(或台)数，增加余热回收内循环泵30的级(或台)数可以是0级、或1级、或2级、或3级、或4级...或n级(n为正整数)等，具体需要增加的级数可以由直接换热余热回收塔29的顶部排出的烟道气28的温度高低来决定；在直接换热余热回收塔29中，冷蓄热流体38吸收烟道气27的热量后转变成热蓄热流体31，其温度接近或低于从底部进入直接换热余热回收塔29的烟道气27的温度，同时冷蓄热流体38还会将烟道气27中的HCl、HF、微小灰尘(包括水溶性和非水溶性，即极性和非极性微小粒子，也就是通常说的PM100和/或PM50和/或PM2.5等各种 粒子)吸附富集，还会将烟道气27中的部分水蒸汽冷凝成水，一同混合在热蓄热流体31中，并从直接换热余热回收塔29的底部排出，经蓄热流体泵32送至蓄热流体沉清槽33中进行沉清，分离出含HCl、HF的灰尘和水34从蓄热流体沉清槽33的底部排出，除尘和除水后的热蓄热流体31由蓄热流体外循环泵35提压送至蓄热流体冷却器37中被冷却水41冷却至常温，并转变成冷蓄热流体38又进入直接换热余热回收塔29中进行重复吸热，同时，冷却水41吸收热量后转变成热水42，其中的热量可以回收使用。
根据图1所示的烟道气脱硫脱硝、脱硫脱硝溶液再生、二氧化硫和/或氮氧化物提浓工艺流程和设备，我们制作和安装了一套小型的模拟工业化烟道气脱硫脱硝装置。该装置中各种设备的规格如下：
吸收塔3规格为φ219×4，总高7.2米，4层填料，每层高的1米，材质316L不锈钢；
贫液槽11规格为φ450×3，总高2.0米，材质316L不锈钢；
冷却器13φ159×3，列管φ10×1，长1.5米，总换热面积为3.9m2，材质316L不锈钢；
热交换器14φ159×3，2台，列管φ10×1，长1.5米，换热面积为2×3.9m2，φ219×3，1台，列管φ6×1，长1.4米，换热面积为9.63m2，总换热面积为2×3.9+9.63＝17.43m2，材质316L不锈钢；
富液加热器17φ159×3，列管φ32×1，长0.9米，总换热面积为1.63m2，材质钛材；
再生塔20规格为φ219×4，总高5.57米，上段一层高1.5米的填料，下端为空塔，材质316L不锈钢；
提浓塔23规格为φ159×4，总高6.2米，上端为钛材列管冷凝器，中段一层填料高1.5米，下段一层填料高2.0米，材质316L不锈钢。
增压风机2型号为2HB710-AH37，送风量318m3/hr，风压-290～390mbar(-29kPa～39kPa)，上海利楷机电设备有限公司；
内循环泵4型号为IHG20-125，流量4.0m3/hr，扬程20米，0.75KW，3台，材质316L不锈钢，上海长申泵业制造有限公司；
富液泵9、脱硫泵10和贫液泵12型号都为IHG25-160，流量4.0m3/hr，扬程32米，1.5KW，各1台，材质316L不锈钢，上海长申泵业制造有限公司；
蒸馏水泵24型号都为WB50/037D，流量1.2m3/hr，扬程14.5米，0.37KW，1台，材质316L不锈钢，广东永力泵业有限公司；
烟道气气体流量计型号为LZB-50玻璃转子流量计，量程范围：50-250m3/hr，江阴市科 达仪表厂；
脱硫脱硝溶液流量计：富液泵、贫液泵和脱硫泵出口液体流量计型号为LZB-32S玻璃管道式流量计，量程范围：0.4-4m3/hr，江阴市科达仪表厂；
吸收塔内循环泵出口液体流量计型号为LZB-25S玻璃管道式流量计，量程范围：0.36-3.6m3/hr，3台，江阴市科达仪表厂；
蒸汽流量计(气提再生塔用)：型号为LUGB-2303-P2涡街流量计，量程范围：8-80m3/hr，北京邦宇诚信工控技术发展有限公司；
蒸汽流量计(提浓塔用)：型号为GHLUGB-25涡街流量计，量程范围：10-60m3/hr，天津光华凯特流量仪表有限公司；
吸收塔3进、出口气体和提浓塔23解析出来的气体成分全部采用连续烟气分析仪在线分析，其中SO2、NO、O2含量采用紫外光JNYQ-I-41型气体分析仪分析，CO2含量采用JNYQ-I-41C型红外线气体分析仪分析，西安聚能仪器有限公司生产；同时，用化学分析法分析和校正气体中SO2、NO、CO2的含量与仪器分析值进行对比，其中用碘量法分析气体中SO2的含量，用氯化钡法分析气体中CO2的含量，用盐酸萘乙二胺比色法分析气体中NO的含量。
用化学方法对脱硫脱硝贫液7、脱硫脱硝富液8和蒸馏水26中的SO2、NO、CO2含量进行分析，其中用碘量法分析溶液中SO2的含量，用氯化钡法分析溶液中CO2的含量，用盐酸萘乙二胺比色法分析溶液中NO的含量。
用空气、SO2、NO和CO2进行配气，气体成分见试验数据表所示。
根据我们的专利技术配置了如下几种脱硫脱硝溶液：
1、15％Na2SO3(w)水溶液；
2、20％柠檬酸一钾盐(w)水溶液；
3、EG溶液；
4、PEG400溶液；
5、PEG400+3％三乙醇胺(w)溶液；
6、NHD溶液(聚合度为4～8的聚乙二醇二甲醚的混合物)；
7、60％EG(w)+30％H2O(w)+10％柠檬酸一钠(w)溶液；
8、60％PEG400(w)+30％H2O(w)+10％柠檬酸一钠盐(w)溶液；
9、30％EG(w)+30％PEG400(w)+30％H2O(w)+10％柠檬酸一钠盐(w)溶液。
用这些脱硫脱硝溶液在以上我们制作和安装的如图1所示的脱硫脱硝装置上，按以上描 述的运行方式进行脱硫脱硝试验。
试验结果表明：
1、当分别用15％Na2SO3(w)水溶液、20％柠檬酸一钾盐(w)水溶液、EG溶液、PEG400溶液进行脱硫脱硝时，一开始溶液吸收二氧化硫能力较强，吸收率达90％以上，但没有吸收氮氧化物的能力，但是经过2至5天不等的连续运行后，溶液逐渐失去吸收二氧化硫的能力，溶液逐渐发生性质的变化，当加热至120℃以上时溶液也无法再生。
2、当分别用PEG400+3％三乙醇胺(w)溶液和NHD溶液进行脱硫脱硝时，一开始溶液吸收二氧化硫能力较强，吸收率达90％以上，吸收氮氧化物的能力也达50％左右，但是经过5至10天不等的连续运行后，溶液逐渐变成褐黑色，吸收二氧化硫和氮氧化物的能力分别降至50％和20％左右，溶液逐渐发生性质的变化，并产生黏性黑色胶状物质。
3、当分别用60％EG(w)+30％H2O(w)+10％柠檬酸一钠(w)溶液、60％PEG400(w)+30％H2O(w)+10％柠檬酸一钠盐(w)溶液和30％EG(w)+30％PEG400(w)+30％H2O(w)+10％柠檬酸一钠盐(w)溶液进行脱硫脱硝时，溶液吸收二氧化硫能力较强，吸收率达90～100％，吸收氮氧化物的能力为40～80％，经过90天的连续运行后，溶液的吸收二氧化硫的能力和吸收氮氧化物的能力不变，脱除二氧化硫和氮氧化物的效率稳定，没有发现溶液发生性质的变化，分别抽取它们的部分运行试验数据分别列入表一、表二和表三中。
从试验结果来看60％EG(w)+30％H2O(w)+10％柠檬酸一钠(w)溶液、60％PEG400(w)+30％H2O(w)+10％柠檬酸一钠盐(w)溶液和30％EG(w)+30％PEG400(w)+30％H2O(w)+10％柠檬酸一钠盐(w)溶液的脱硫脱硝的效果相差不大，效果比较理想，溶液也比较稳定。
试验结果提示，我们前期提出专利申请的“改性聚乙二醇脱除气体中SOx的方法”(申请号201310409296.8)、“复合醇胺类溶液脱除气体中SOx的方法”(申请号：201310481557.7)、“乙二醇类复合溶液脱除气体中SOx的方法”(申请号：201310682799.2)和“多元醇复合溶液脱除气体中SOx的方法”(申请号：201310682382.6)等技术所指导的脱硫溶液不仅具有脱除气体中二氧化硫的能力，还具有吸收气体中氮氧化物的能力。尤其，向这些溶液中添加少量的含亚砜和/或砜基团的添加剂(如DMSO和/或环丁砜，或它们的羟基和/或羧基取代物)时，溶液吸收氮氧化物的能力大幅提高。因此，利用这些溶液在本发明所述的工艺和设备中可以进行大规模工业化用于烟道气和/或废气的脱硫和脱硝。
表一.60％EG(w)+30％H2O(w)+10％柠檬酸一钠(w)溶液为脱硫脱硝溶液时的运行数据(2014年5月6日～14日数据摘录)
Figure PCTCN2015080761-appb-000005
表二.60％PEG400(w)+30％H2O(w)+10％柠檬酸一钠盐(w)溶液为脱硫脱硝溶液时的运行数据(2014年5月18至21日，每天2组，21日3组数据)
Figure PCTCN2015080761-appb-000006
表三.30％EG(w)+30％PEG400(w)+30％H2O(w)+10％柠檬酸一钠盐(w)溶液为脱硫脱硝溶液时的运行数据(2014年5月23日至31日摘录数据)
Figure PCTCN2015080761-appb-000007

Claims (10)

  1. 一种烟道气脱硫脱硝工艺，包括以下过程：
    1)余热回收过程：采用换热回收方式将烟道气的温度降至50℃以下，并进行余热回收；
    2)脱硫脱硝过程：降温后的烟道气进入吸收塔中，通过脱硫脱硝溶液吸收其中的二氧化硫和/或氮氧化物，所述脱硫脱硝溶液为含多醇类和/或聚多醇类的复合溶液；
    3)脱硫脱硝溶液再生过程：吸收了二氧化硫和/或氮氧化物的脱硫脱硝溶液在再生塔中通过加热和/或气提和/或真空再生方式释放出二氧化硫和/或氮氧化物，再生后的脱硫脱硝溶液循环使用；
    4)二氧化硫和/或氮氧化物提浓过程：脱硫脱硝溶液再生过程释放出来的二氧化硫和/或氮氧化物经提浓塔浓缩成较高纯度的二氧化硫和/或氮氧化物产品。
  2. 如权利要求1所述的烟道气脱硫脱硝工艺，其特征在于，所述余热回收过程采用直接换热回收方式，或者间接换热和直接换热同时回收的方式。
  3. 如权利要求2所述的烟道气脱硫脱硝工艺，其特征在于，在所述余热回收过程中，烟道气与蓄热流体直接接触进行换热，通过设置一级或多级内循环泵增加蓄热流体循环量。
  4. 如权利要求1所述的烟道气脱硫脱硝工艺，其特征在于，在所述脱硫脱硝过程中，通过设置一级或多级内循环泵增加脱硫脱硝溶液的循环量。
  5. 如权利要求1所述的烟道气脱硫脱硝工艺，其特征在于，所述脱硫脱硝溶液再生过程具体是：吸收了烟道气中的二氧化硫和/或氮氧化物的脱硫脱硝溶液为脱硫脱硝富液，先与从再生塔底部流出的脱硫脱硝贫液进行间接式热交换，又被加热至90℃以上，然后从再生塔上端进入，通过加热和/或气提和/或真空再生方式，解析出二氧化硫和/或氮氧化物，成为脱硫脱硝贫液，从再生塔底部流出，经热交换和冷却至50℃以下后送至脱硫脱硝过程循环利用。
  6. 如权利要求1所述的烟道气脱硫脱硝工艺，其特征在于，所述二氧化硫和/或氮氧化物提浓过程具体是：脱硫脱硝溶液再生过程释放出来的包含二氧化硫和/或氮氧化物的混合气体从提浓塔的中段进入，和提浓塔顶部冷凝下来的水逆流接触，将混合气体中的水蒸汽冷凝下来，除去水蒸汽的混合气体从提浓塔顶部流出；水蒸汽从提浓塔底端进入，和冷凝下来的水逆流接触，水蒸汽将冷凝水中的残余二氧化硫和/或氮氧化物提出来，使冷凝水变 成蒸馏水，从提浓塔底部流出并回收。
  7. 一种烟道气脱硫脱硝设备，包括余热回收塔、吸收塔、再生塔和提浓塔，其中：余热回收塔：用于使烟道气与蓄热流体进行换热，将烟道气的温度降至50℃以下，并进行余热回收；
    吸收塔：用于使降温后的烟道气与脱硫脱硝溶液直接接触，脱硫脱硝溶液吸收烟道气中的二氧化硫和/或氮氧化物成为脱硫脱硝富液，然后从吸收塔排出；所述脱硫脱硝溶液为含多醇类和/或聚多醇类的复合溶液；
    再生塔：用于使脱硫脱硝富液通过加热和/或气提和/或真空再生方式解析出二氧化硫和/或氮氧化物成为脱硫脱硝贫液，再生得到的脱硫脱硝贫液又送回吸收塔循环利用；
    提浓塔：用于将再生塔释放出来的包含二氧化硫和/或氮氧化物的混合气体中的水蒸汽通过冷凝去除，二氧化硫和/或氮氧化物则浓缩成较高纯度的二氧化硫和/或氮氧化物产品。
  8. 如权利要求7所述的烟道气脱硫脱硝设备，其特征在于，所述余热回收塔设置有一级或多级用于增加蓄热流体循环量的内循环泵。
  9. 如权利要求7所述的烟道气脱硫脱硝设备，其特征在于，所述吸收塔设置有一级或多级用于增加脱硫脱硝溶液循环量的内循环泵。
  10. 如权利要求7所述的烟道气脱硫脱硝设备，其特征在于，在所述吸收塔与再生塔之间设置热交换器，来自吸收塔的脱硫脱硝富液与从再生塔流出的脱硫脱硝贫液通过该热交换器进行间接式热交换。
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Publication number Priority date Publication date Assignee Title
US7991363B2 (en) 2007-11-14 2011-08-02 Paratek Microwave, Inc. Tuning matching circuits for transmitter and receiver bands as a function of transmitter metrics
US9026062B2 (en) 2009-10-10 2015-05-05 Blackberry Limited Method and apparatus for managing operations of a communication device
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CN114392639B (zh) * 2021-12-29 2023-07-14 中石化宁波工程有限公司 一种催化裂化烟气余热利用耦合脱硫湿烟雨消除工艺
CN115090108A (zh) * 2022-06-17 2022-09-23 天津铁厂有限公司 一种降低焦炉烟气氮氧化物的处理装置及工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1780678A (zh) * 2003-08-13 2006-05-31 坎索尔夫科技公司 低能耗so2洗涤方法
CN101185838A (zh) * 2007-08-24 2008-05-28 中国石油化工集团公司 一种可再生湿法烟气脱硫工艺
CN101896247A (zh) * 2007-12-13 2010-11-24 阿尔斯托姆科技有限公司 用于再生吸收剂溶液的系统和方法
CN102343201A (zh) * 2011-10-11 2012-02-08 南京大学 一种利用烟道气余热脱除其酸性气体的工艺

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3767777A (en) 1972-02-23 1973-10-23 Trentham Corp Method of separating sulfur dioxide from gaseous mixtures
JPS5228111B2 (zh) * 1973-02-22 1977-07-25
JPS52119487A (en) * 1976-04-01 1977-10-06 Mitsui Petrochem Ind Ltd Removal of nitrogen oxide in exhaust gas
JPS5316384A (en) * 1976-07-30 1978-02-15 Hidetoshi Tsuchida Gas adsorbents
US4418044A (en) * 1982-01-15 1983-11-29 Conoco Inc. Nitric oxide and sulfur oxide absorption by scrubbing with Fe++ /S.sub. O3-
DE3612123A1 (de) 1985-09-27 1987-04-09 Linde Ag Verfahren zum auswaschen von no und/oder so(pfeil abwaerts)2(pfeil abwaerts) aus gasgemischen
CN1067292C (zh) * 1996-04-19 2001-06-20 东南大学 一种易再生烟气脱硫脱硝剂及其制备、再生方法
US7056482B2 (en) * 2003-06-12 2006-06-06 Cansolv Technologies Inc. Method for recovery of CO2 from gas streams
US8318116B2 (en) * 2006-04-07 2012-11-27 Liang Hu Methods for deacidizing gaseous mixtures by phase enhanced absorption
CN100490943C (zh) * 2007-02-09 2009-05-27 中北大学 含氮氧化物废气的处理装置
CN101053746B (zh) 2007-06-06 2010-06-09 北京大学 乙二醇脱除烟道气中sox的方法
CN101502741B (zh) 2009-02-16 2011-01-05 北京博源恒升高科技有限公司 聚乙二醇脱除气体中SOx的方法
CN102091503B (zh) * 2011-01-05 2015-10-07 湖南大学 一种捕集、固定和净化二氧化碳、二氧化硫、三氧化硫和氮氧化物的化学方法
JP5968159B2 (ja) * 2012-08-20 2016-08-10 三菱重工業株式会社 Ｃｏ２回収装置およびｃｏ２回収方法
CN103143248A (zh) * 2013-02-08 2013-06-12 珠海共同机械设备有限公司 工业废气中低含量二氧化碳吸收及解析系统
CN103432890B (zh) 2013-09-10 2015-12-09 北京博源恒升高科技有限公司 改性聚乙二醇脱除气体中SOx的方法
CN103495340B (zh) 2013-10-15 2015-11-18 北京博源恒升高科技有限公司 复合醇胺类溶液脱除气体中SOx的方法
CN103611391B (zh) * 2013-12-12 2016-01-20 北京博源恒升高科技有限公司 乙二醇类复合溶液脱除气体中SOx的方法
CN103623689B (zh) * 2013-12-12 2016-06-29 北京博源恒升高科技有限公司 多元醇复合溶液脱除气体中SOx的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1780678A (zh) * 2003-08-13 2006-05-31 坎索尔夫科技公司 低能耗so2洗涤方法
CN101185838A (zh) * 2007-08-24 2008-05-28 中国石油化工集团公司 一种可再生湿法烟气脱硫工艺
CN101896247A (zh) * 2007-12-13 2010-11-24 阿尔斯托姆科技有限公司 用于再生吸收剂溶液的系统和方法
CN102343201A (zh) * 2011-10-11 2012-02-08 南京大学 一种利用烟道气余热脱除其酸性气体的工艺

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3153224A4 *

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106039969A (zh) * 2016-07-21 2016-10-26 黄立维 一种二氧化硫的吸收方法及装置
CN106268305A (zh) * 2016-09-28 2017-01-04 陈和平 焦炉烟气脱硫脱硝装置
CN107036115A (zh) * 2017-05-26 2017-08-11 山西大学 一种深度利用锅炉烟气余热以及污染物脱除的系统
CN107036115B (zh) * 2017-05-26 2023-05-26 山西大学 一种深度利用锅炉烟气余热以及污染物脱除的系统
CN107991885A (zh) * 2017-12-28 2018-05-04 华能吉林发电有限公司长春热电厂 一种燃煤电厂脱硝喷氨自动控制方法及系统
CN108706784B (zh) * 2018-08-03 2023-05-16 山东大学 一种处理烧结烟气脱硫脱硝废水的系统和方法
CN108706784A (zh) * 2018-08-03 2018-10-26 山东大学 一种处理烧结烟气脱硫脱硝废水的系统和方法
CN109569246A (zh) * 2018-12-27 2019-04-05 河南海力特机电制造有限公司 高压细水雾脱硫装置
CN109821371B (zh) * 2019-03-25 2024-03-22 郑州大学 一种燃气窑炉用氮氧化物减排装置及其方法
CN109821371A (zh) * 2019-03-25 2019-05-31 郑州大学 一种燃气窑炉用节能环保型氮氧化物减排装置及其方法
CN112403182A (zh) * 2019-11-05 2021-02-26 中冶长天国际工程有限责任公司 一种解析塔及烟气加热系统
CN112403182B (zh) * 2019-11-05 2022-12-02 中冶长天国际工程有限责任公司 一种解析塔及烟气加热系统
CN112619393A (zh) * 2020-11-17 2021-04-09 天津浩创节能环保设备有限公司 一种锅炉烟气脱硫脱硝系统
CN113144772A (zh) * 2021-04-30 2021-07-23 青铜峡铝业股份有限公司宁东铝业分公司 一种两段式电解烟气净化排放装置、控制系统及方法
CN113144772B (zh) * 2021-04-30 2022-10-14 青铜峡铝业股份有限公司宁东铝业分公司 一种两段式电解烟气净化排放装置、控制系统及方法
CN114797416A (zh) * 2022-04-19 2022-07-29 成都艾侃智能设备有限公司 一种污泥焚烧尾气超低排放处理的方法
CN114797713A (zh) * 2022-05-13 2022-07-29 中国科学院过程工程研究所 一种微波强化碳还原废硫酸的方法
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