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WO2016150302A1 - 一种脱硫脱硝剂 - Google Patents

一种脱硫脱硝剂 Download PDF

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Publication number
WO2016150302A1
WO2016150302A1 PCT/CN2016/075922 CN2016075922W WO2016150302A1 WO 2016150302 A1 WO2016150302 A1 WO 2016150302A1 CN 2016075922 W CN2016075922 W CN 2016075922W WO 2016150302 A1 WO2016150302 A1 WO 2016150302A1
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Prior art keywords
desulfurization
acid
gas
denitration
denitration agent
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PCT/CN2016/075922
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English (en)
French (fr)
Inventor
魏雄辉
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江西永丰县博源实业有限公司
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Priority to ES16767679T priority Critical patent/ES2939178T3/es
Priority to JP2017548018A priority patent/JP6538185B2/ja
Priority to CA2978198A priority patent/CA2978198C/en
Priority to EA201791808A priority patent/EA033678B1/ru
Priority to BR112017018682-9A priority patent/BR112017018682B1/pt
Priority to KR1020177026521A priority patent/KR102009162B1/ko
Priority to EP16767679.0A priority patent/EP3272413B1/en
Priority to AU2016236624A priority patent/AU2016236624B2/en
Priority to PL16767679.0T priority patent/PL3272413T3/pl
Priority to MX2017012046A priority patent/MX2017012046A/es
Application filed by 江西永丰县博源实业有限公司 filed Critical 江西永丰县博源实业有限公司
Priority to US15/555,810 priority patent/US10124289B2/en
Publication of WO2016150302A1 publication Critical patent/WO2016150302A1/zh
Priority to ZA2017/06322A priority patent/ZA201706322B/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur 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
    • B01D53/14—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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/507—Sulfur oxides by treating the gases with other liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • 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
    • B01D2252/2023—Glycols, diols or their derivatives
    • B01D2252/2025—Ethers or esters of alkylene glycols, e.g. ethylene or propylene carbonate
    • 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
    • B01D2252/2023—Glycols, diols or their derivatives
    • B01D2252/2026—Polyethylene glycol, ethers or esters thereof, e.g. Selexol
    • 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
    • B01D2252/2023—Glycols, diols or their derivatives
    • B01D2252/2028—Polypropylene glycol, ethers or esters thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0258—Other waste gases from painting equipments or paint drying installations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention relates to the field of gas desulfurization and/or denitrification industry, in particular to a desulfurization and denitration agent for flue gas or various combustion tail (waste) gas desulfurization and/or 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. Therefore, the research on flue gas desulfurization and denitrification is quite urgent and challenging.
  • 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 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.
  • the dry desulfurizer is extremely expensive and expensive, and at the same time, a large amount of waste residue needs to be deposited and landfill, which may cause serious pollution transfer and secondary pollution.
  • the desulfurizing agent used in the wet desulfurization process is mainly calcium carbonate, magnesium carbonate, calcium oxide, magnesium oxide, ammonia, sodium sulfite (or potassium) and an organic acid-organic acid salt buffer solution.
  • the desulfurization process is to grind calcium carbonate, magnesium carbonate, calcium oxide and magnesium oxide into a fine powder having a mesh size of more than 325 mesh, and then formulate it into a slurry containing 10% to 15% of calcium carbonate powder; the slurry is in the absorption tower.
  • the sulfur dioxide in the gas and the calcium carbonate in the slurry, or magnesium carbonate, or calcium oxide, or magnesium oxide react to form calcium sulfite or magnesium sulfite.
  • 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 a calcium sulfate slurry; the calcium sulfate slurry flows out of the absorption tower, and enters the separator to separate the calcium sulfate in the slurry; the separated water Return to the preparation of calcium carbonate slurry, recycling; the separated calcium sulfate is either used as a waste landfill or road repair, or used to make gypsum board after purification.
  • this process produces a lot of solid calcium sulfate, which also contains solid waste such as calcium sulfite and unreacted calcium carbonate.
  • the limestone consumption is large, the crushing and milling equipment is huge, the power consumption is high, the investment is large, and During the absorption process, solid sediments are generated, which may cause blockage of equipment, discharge of sewage is large, and secondary pollution is serious.
  • the magnesium sulphate slurry is precipitated and enters the separator to separate the magnesium sulphate from the slurry; the separated water is returned for preparation of the magnesium oxide slurry and recycled; the separated magnesium sulphate is calcined above 1235K to form magnesium oxide and The gas is sulphur dioxide, the produced magnesium oxide is reused, and the sulphur 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.
  • the slurry of calcium carbonate, magnesium carbonate, calcium oxide and magnesium oxide contains tiny hydrophilic and non-hydrophilic particles (mainly calcium salt particles, aluminum salt particles, magnesium salt particles, titanium salt particles, iron salts). 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.) It is taken out by the flue gas and discharged into the atmosphere.
  • tiny hydrophilic and non-hydrophilic particles mainly calcium salt particles, aluminum salt particles, magnesium salt particles, titanium salt particles, iron salts.
  • ammonia desulfurization process uses ammonia as a desulfurizing agent, and 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, and finally ammonium hydrogen sulfate.
  • Ammonia is alkalized into ammonium sulfate, and ammonium sulfate is separated as a by-product of fertilizer.
  • 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, causing secondary pollution of atmospheric ammonia.
  • ammonia is large, and ammonia is converted into Low-value ammonium sulfate, high desulfurization cost, and easy to produce clogging equipment and pipelines; and ammonia is highly corrosive, equipment corrosion is serious, and ammonia production process is a process of high energy consumption and high pollution. Excessive consumption of ammonia is also indirect. Increase the process of environmental pollution and increase energy consumption, so the use of ammonia should be minimized.
  • the seawater desulfurization process utilizes a salt containing a large amount of calcium, magnesium, aluminum, sodium, potassium ions in seawater, especially carbonate as a desulfurizing agent, and these desulfurizing agents react with sulfur dioxide to produce sulfite; seawater absorbed by sulfur dioxide After exposure and oxidation, 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) method is a sodium sulfite (or potassium) desulfurizing agent, and an aqueous solution thereof is contacted with the flue gas in an absorption tower, and 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 bisulfite (or potassium) solution is heated and regenerated
  • sodium bisulfite (or potassium) solution is converted into sodium sulfite (or potassium) solution
  • sulfur dioxide is released; sodium sulfite (or potassium) aqueous solution is recycled, and sulfur dioxide gas can be recovered as a by-product.
  • the method is better, but the actual test shows that the sodium bisulfite (or potassium) solution has a very low regeneration rate, and only a very small part of sodium bisulfite (or potassium) can be converted into sodium sulfite (or potassium).
  • Sodium bisulfate (or potassium) cannot be decomposed and the steam consumption is large. Therefore, the law has not been able to achieve industrialization.
  • Wellman-Lord desulfurization 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 is a buffer solution composed of an organic acid and an organic acid salt as a desulfurization liquid, which is contacted with the flue gas in the absorption tower, and the sulfur dioxide in the gas reacts with the organic acid salt in the solution to form sulfurous acid. Hydrogen salt and organic acid; the solution is regenerated by heating, the sulfite in the solution is converted into an organic acid salt, and the solution is still converted into an organic acid-organic acid salt buffer solution, which is repeatedly used, and at the same time, sulfur dioxide is released, and the sulfur dioxide gas can be recovered as by-product.
  • the method is better, but the actual test shows that in the organic acid-organic acid salt buffer solution, the regeneration rate of sulfite in steam heating is very low, only a very small part of sulfite can be converted into organic acid salt, most of the sub- Sulfate cannot be decomposed and the amount of steam consumed is large, so the method has not been industrialized.
  • calcium oxide or calcium hydroxide
  • the organic acid salt buffer solution is recycled, but the actual desulfurizing agent in the process is also calcium oxide (or calcium hydroxide). Because the solution contains some calcium ions, it will precipitate during the desulfurization process, blocking the pipeline and equipment.
  • the denitration processes currently used in actual production mainly include selective catalytic reduction (SCR) or selective non-catalytic reduction (SNCR).
  • SCR Selective catalytic reduction
  • the flue gas is mixed with ammonia or urea injection, after mixing through the catalyst layer, the selective NO X conversion (reduction) of N 2 and H 2 O.
  • the SCR method is currently the most mature denitration technology with the highest denitrification efficiency.
  • the first SCR system demonstration project was established at the Shimoneski power plant in Japan, and the SCR technology was widely used in Japan. Europe has experienced more than 120 successful application in large-scale apparatus, the removal rate of NO X which may reach 80% to 90%.
  • Japan has about 170 sets of equipment, such equipment close to the 100GW installed capacity of power plants, the US government will also SCR technology as the main technical main power plant control NO X, the method has been reported that the SCR denitration plants at home and abroad More mature mainstream technology.
  • the SCR method for flue gas denitration is based on a catalyst containing TiO 2 and V 2 O 5 as a main component, at a temperature of 280-400 ° C, or a catalyst containing TiO 2 , V 2 O 5 and MnO as main components. Under catalysis, at more than 180 ° C, ammonia is sprayed into the flue gas, and NO and NO 2 are reduced to N 2 and H 2 O to achieve the purpose of denitration.
  • SNCR denitration technology is a selective non-catalytic reduction technology. It is a catalyst that does not use a catalyst to inject an amino group-containing reducing agent (such as ammonia, urea solution, etc.) at a temperature range of 850 to 1100 °C. In the furnace, NO and NO 2 in the flue gas are reduced to N 2 and H 2 O to achieve the purpose of denitration. But NO X removal industrial SNCR system is only 30-70%.
  • an amino group-containing reducing agent such as ammonia, urea solution, etc.
  • the catalyst used in the denitration process will be contaminated by high concentration of soot, abrasion and impurities in the fly ash. If the temperature of the flue gas is too high, the catalyst will be sintered and deactivated. The presence of SO 2 will cause a rapid decrease in catalyst activity. .
  • Ozone needs to consume about 10 kWh of electricity and 10-20 kg of pure oxygen respectively; energy consumption is high, consumption is high, and investment is large, so that ozone flue gas desulfurization and denitration technology cannot achieve large-scale industrialization.
  • CN101352645A discloses a catalytic oxidative denitration process, wherein TiO 2 or ZrO 2 -TiO 2 is used as a carrier, and Co is a catalyst of active components, and NO is oxidized into NO 2 which is easily soluble in water by using oxygen contained in the flue gas. Thereafter, the nitrogen oxides are removed by absorption with an alkali solution.
  • CN1768902A discloses a boiler flue gas denitration method, which sprays ozone O 3 in a low temperature section of a boiler flue having a temperature range of 110-150 ° C, and oxidizes nitric oxide NO in the boiler flue gas into a high-valent nitrogen which is easily soluble in water.
  • the oxide NO 2 , NO 3 or N 2 O 5 , the molar ratio of the injected ozone O 3 to the NO in the boiler flue gas is 0.5 to 1.5, and then washed with alkali water to remove nitrogen oxides in the flue gas.
  • the denitration efficiency is low, and the ozone consumption is extremely high.
  • the emission standard is reached, the operation cost is particularly high, and the enterprise cannot bear it, so the technology has been unable to achieve large-scale industrialization.
  • the invention provides a flue gas desulfurization and denitration agent, which is obtained by mixing a polyol and/or a polypolyol substance, a polycarboxylic acid substance and an alkaline substance, and heating under the condition of heating to 90 ° C or higher. substance.
  • a flue gas desulfurization and denitration agent which is obtained by mixing a polyol and/or a polypolyol substance, a polycarboxylic acid substance and an alkaline substance, and heating under the condition of heating to 90 ° C or higher. substance.
  • the polyol and/or the polyhydric alcohol, the polycarboxylic acid, and the basic substance are mixed and condensed and/or polymerized, the hydroxyl group and the hydroxyl group or the hydroxyl group and the carboxyl group condense to lose a water molecule to form a macromolecule or a high
  • the ethers and/or esters of the molecule, while the carboxyl groups in the molecule are
  • the polyalcohol refers to an organic compound (containing phenols) having two or more hydroxyl groups in the molecule, such as ethylene glycol, propylene glycol, 1,2,3-propanetriol (glycerol), 1,2 (or 1,3 or 1,4 or 2,3)-butanediol, 1,4-butenediol, pentanediol, neoisopentyl glycol, isoprene glycol, 1,5- Pentylene glycol, 1,6-hexanediol, benzenediol, 1,2,4-butanetriol, isobutyltriol, pentanetriol, isobatriol, benzenetriol, pentaerythritol, pentaerythritol, Isopentanol, butyltetral, gallic acid, tannin, and the like.
  • the polypolyol is a polymer or a macromolecular substance, wherein a hydroxyl group in one polyol molecule condenses with a hydroxyl group in another polyol molecule to lose a water molecule to form an ether bond, which is ether-bonded.
  • the molecularly linked molecules are called polyalcohols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypropanol and polybutanol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene. Glycol monoethyl ether, polyethylene glycol diethyl ether, and the like.
  • the polycarboxylic acid substance is a compound containing at least two or more carboxyl groups in the same molecule, such as oxalic acid, malonic acid, succinic acid, amino oxalic acid, ammonia triacetic acid, EDTA, tartaric acid. , phthalic acid, poly gallic acid and citric acid.
  • the alkaline substance comprises an inorganic basic substance and/or an organic basic substance.
  • the inorganic alkaline substance includes hydroxides, carbonates, carboxylates, complexes, and ammonia of alkali metals, alkaline earth metals or transition metals; preferably hydroxides containing Li, Na, K, Mg or Ca Matter, carbonate.
  • the organic alkaline substance is mainly an organic amine substance, and the organic amine is selected from the group consisting of organic amines.
  • Fatty amines, aromatic amines and alcohol amines, such as fatty amines are selected from the group consisting of: methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, n-propylamine.
  • the desulfurization and denitration agent is prepared by mixing a polyol and/or a polypolyol, a polycarboxylic acid and a basic substance in a certain ratio, and then heating to above 90 ° C, after esterification and/or etherification reaction.
  • a type of macromolecular or polymeric ether and/or ester material formed; the ratio is: polyol and/or polypolyol: polycarboxylic acid: basic substance molar ratio: 10:0.5 ⁇ 2:0.1 ⁇ 3, preferably 1:0.7 ⁇ 1:0.3 ⁇ 2, more preferably 1:0.9 ⁇ 1.3:0.5 ⁇ 1.5, very preferably 1:0.9 ⁇ 1.1:0.5 ⁇ 1.2, most preferably 1: 1:0.5 to 1.
  • the desulfurization and denitration agent of the present invention Adding the desulfurization and denitration agent of the present invention to a solution composed of ethylene glycol and/or polyethylene glycol and/or water to form the desulfurization and denitration solution of the present invention, wherein the desulfurization and denitration agent is used in an amount of 0.1 to 50% by weight, preferably 2 30 wt%, more preferably 5-25 wt%, most preferably 10-20 wt%.
  • the desulfurization and denitrification of the solution can be used simultaneously remove SO X in the exhaust gas and NO X, can also be used separately to remove SO X in the exhaust gas (including SO 2 and SO 3), or for the removal of exhaust gases alone the X-NO (including NO and NO 2).
  • ethylene glycol, citric acid and sodium hydroxide, polyethylene glycol, citric acid and sodium hydroxide, ethylene glycol, citric acid and N-A are described below.
  • the four reaction formulas of dimethyldiethanolamine (MDEA), polyethylene glycol, citric acid and N-methyldiethanolamine (MDEA) are taken as an example to illustrate the synthesis method of the desulfurization and denitration agent of the present invention.
  • esterification process of polyethylene glycol, citric acid and sodium hydroxide is as follows:
  • Ethylene glycol, citric acid and N-methyldiethanolamine can undergo the following etherification and esterification processes:
  • the esterification process is as follows:
  • N-methyldiethanolamine can be used as an organic base instead of the above-mentioned NaOH and citric acid, and then etherified with ethylene glycol.
  • Polyethylene glycol, citric acid and N-methyldiethanolamine (MDEA) can undergo the following etherification and esterification processes:
  • the esterification process is as follows:
  • the synthetic formulations listed above are not intended to limit the desulfurization and denitration agents of the present invention to be synthesized only with ethylene glycol and/or polyethylene glycol, citric acid, sodium hydroxide and/or MDEA, but with polyols and/or polyatoms.
  • Alcohols, polycarboxylic acids and basic substances are mixed in a certain ratio and then heated to above 90 ° C.
  • alkaline substances include inorganic alkaline substances and organic alkaline substances. After the esterification and/or etherification reaction, the color of the liquid changes from colorless to a yellow-brown, viscous liquid with a marked increase in boiling point.
  • the reaction process is a polyol and/or a polyhydric alcohol and a hydroxyl group-containing polycarboxylic acid and/or
  • the condensation of a hydroxyl group or a carboxyl group in a polycarboxylic acid substance loses a water molecule and is condensed to synthesize a macromolecular or high molecular ether and/or ester desulfurization and denitrification agent substance.
  • the carboxyl group and the inorganic group in the desulfurization and denitration agent molecule Cationic bonding of a basic substance may be any cation such as a hydrogen ion, an ammonium ion, a sodium ion, a potassium ion, a transition metal ion, or the like).
  • the above-mentioned polyol refers to an organic compound (containing a phenol) having two or more hydroxyl groups in the molecule, such as ethylene glycol, propylene glycol, 1,2,3-propanetriol (glycerol), 1,2 or 1,3 or 1,4 or 2,3)-butanediol, 1,4-butenediol, neoisopentyl glycol, pentaerythritol, 1,5-pentanediol, 1,6- Hexanediol, 1,2,4-butanetriol, butanol, diethylene glycol diether, benzenediol, benzenetriol, gallic acid, tannin, etc.; the polypolyol is high A molecule or a macromolecular substance in which a hydroxyl group in one polyol molecule condenses with a hydroxyl group in another polyol molecule to lose a water molecule to form an ether bond.
  • the polypolyol is
  • the molecule linked by an ether bond is a polyalcohol substance.
  • the hydroxyl group-containing polycarboxylic acid is a compound containing at least one hydroxyl group in the same molecule and containing two or more carboxyl groups, such as tannin Poly-galic acid, citric acid, hydroxy fatty acid, hydroxy terephthalic acid, hydroxyphthalic acid, hydroxyisophthalic acid, hydroxybenzenetricarboxylic acid, polyhydroxyl Tricarboxylic acid and other hydroxyaromatic polyacids and polyhydroxyaromatic polyacids; said polycarboxylic acid species having at least two or more carboxyl compounds in the same molecule, such as EDTA, oxalic acid, C Diacid, succinic acid, amino oxalic acid, ammonia triacetic acid, fatty polyacids, terephthalic acid, phthalic acid, isophthal
  • the reaction process is a polyol and/or a polyhydric alcohol and a hydroxyl group-containing polycarboxylic acid and/or The condensation of a hydroxyl group or a carboxyl group in a polycarboxylic acid substance to lose a water molecule and then condense to synthesize a macromolecular or high molecular ether and/or ester desulfurization denitrification substance, such desulfurization
  • a carboxyl group and an organic basic substance in the molecule of the denitrizer are combined in the form of an organic cation.
  • the organic alkaline substance is an organic amine substance, and the organic amine is selected from the group consisting of a fatty amine, an aromatic amine, and an alcohol amine.
  • the fatty amine is selected from the group consisting of methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, n-propylamine, isopropylamine, monobutylamine, and dibutylamine.
  • the desulfurization and denitration agent of the present invention has the following advantages: 1 conventional desulfurization and/or denitration agent and An irreversible reaction of sulfur dioxide or nitrogen oxides, the by-products of which are calcium sulfate and calcium sulfite, or ammonium sulfate and ammonium sulfite, nitrogen and water, the flue gas desulfurization denitration agent of the present invention and sulfur dioxide and/or nitrogen oxides.
  • the reversible reaction of weak combination, after stripping regeneration, the desulfurization and denitration agent restores the original structure, and releases sulfur dioxide and/or nitrogen oxides, and the by-products are high-purity sulfur dioxide and/or nitrogen oxides (or nitrates).
  • the flue gas desulfurization and denitration agent of the present invention It is a high-boiling, non-toxic, harmless and highly safe ether and/or ester polymer compound with strong chemical stability, high boiling point and full cycle use.
  • 3 traditional wet desulfurizer is calcium carbonate or calcium oxide, which requires the use of a large amount of mineral calcium carbonate 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 elements Mineral particles such as silica particles, mullite particles, silicate particles, and phosphate particles are emitted together into the atmosphere by flue gas, and the surface of these particles easily adsorbs sulfur dioxide, sulfur trioxide, hydrogen chloride, and hydrogen fluoride.
  • 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 elements
  • Mineral particles such as silica particles, mullite particles, silicate particles, and phosphate particles are
  • the flue gas desulfurization denitration agent of the present invention is used for flue gas or exhaust gas desulfurization and denitrification without such a phenomenon, as the invention is widely used to eliminate smog and atmospheric photochemical reaction phenomenon; 4 the traditional desulfurizer or denitrification agent is The one-time use is high in operation cost and cannot produce economic benefits.
  • the flue gas desulfurization and denitration agent of the invention has low operation cost, high desulfurization and denitration efficiency, and at the same time converts waste into valuable chemical raw materials, which can generate large economic benefits. , social and environmental benefits; 5 traditional wet desulfurization and / or denitrification agents are suitable for lower sulfur content or low Oxygen content gas desulfurization and/or denitrification, the flue gas desulfurization denitration agent of the invention can be used for desulfurization and/or denitration of low sulfur content and/or low nitrogen oxide content gas, and can also be used for high sulfur content And/or desulfurization and/or denitrification of high nitrogen oxide content gases.
  • the flue gas desulfurization and denitration agent of the invention has high purification degree of desulfurization and denitration, and can stably reduce the content of total sulfur and nitrogen oxides in the gas to 30 mg/m 3 or less, and the boiling point of the solution is high and the loss is small.
  • the gas-liquid ratio of desulfurization and denitration is large, the energy consumption is low, the operation cost is low, and the operation is simple.
  • the flue gas desulfurization and denitration agent of the invention has wide industrial use, and can be used for simultaneously removing sulfur dioxide and nitrogen oxides in a gas, and can also be used for separately removing sulfur dioxide in a 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 waste gas containing SOx for desulfurization and/or denitrification.
  • the content of total sulfur and/or total nitrogen oxides in the gas and/or nitrogen oxide-containing gas is less than 99.9% by volume.
  • Figure 1 is a schematic diagram of a process and equipment for simulating flue gas desulfurization and denitration.
  • 1 is the booster fan
  • 2 is the absorption tower
  • 3 is the desulfurization pump
  • 4 is the rich liquid pump
  • 5 is the lean liquid tank
  • 6 is the lean liquid pump
  • 7 is the cooler
  • 8 is the heat exchanger
  • 9 It is a rich liquid heater
  • 10 is a regeneration tower
  • 11 is a concentration tower
  • 12 is a pre-purification flue gas
  • 13 is a purified flue gas
  • 14 is a lean liquid
  • 15 is a rich liquid
  • 16 is a regenerated analytical gas
  • 17 It is steam for stripping
  • 18 is concentrated sulfur dioxide and/or nitrogen oxide gas
  • 19 is condensed hot water
  • 20 is cooling water
  • 21 is a heating medium.
  • F 1 , F 2 , F 3 , and F 4 represent the flow rate of the flue gas 12 before purification, the flow rate of the desulfurized lean liquid 14, and the steam flow rate into the regeneration tower 10, respectively.
  • a 1 is the composition of the flue gas 12 before purification
  • a 2 is the composition of the flue gas 13 after purification
  • a 3 is the composition of the concentrated sulfur dioxide and/or nitrogen oxide gas 18
  • a 4 is the SO 2 and NO content (including pH) in the rich liquid 15
  • a 5 is the content of SO 2 and NO in the lean liquid 14 (including the pH value)
  • a 6 is the SO in the condensed hot water 19 2 and NO content
  • P 1 is the bottom pressure of the absorption tower 2
  • P 2 is the top pressure of the absorption tower 2
  • P 3 is the pressure in the regeneration tower 10
  • P 4 is the pressure of the steam 17 for stripping
  • P 5 is the concentration tower 11
  • T 1 is the temperature at the bottom of the absorption tower 2
  • T 2 is the temperature at the top of the absorption tower 2
  • T 3 is the temperature in the regeneration tower 10
  • T 4 is the temperature of the steam 17 for stripping
  • T 5 is the concentration column temperature 11, T 6 a concentrated sulfur dioxide and / or
  • the desulfurization and denitration agent of the present invention is dissolved in ethylene glycol or polyethylene glycol to form a desulfurization and denitration solution (lean solution 14), injected into the lean liquid tank 5, and all equipment is turned on for operation.
  • the operation method is as follows:
  • the pre-purification flue gas 12 whose temperature is lower than 80 ° C (the optimum temperature is below 35 ° C) is pressurized by the booster fan 1 and enters the absorption tower 2 from the bottom, while the lean liquid 14 enters from the top.
  • the pre-purification flue gas 12 and the lean liquid 14 are in direct contact, and at this time, the sulfur dioxide and/or nitrogen oxides and a small amount of carbon dioxide in the flue gas 12 before purification are absorbed by the lean liquid 14
  • the pre-purification flue gas 12 which has absorbed sulfur dioxide and/or nitrogen oxides and a small amount of carbon dioxide is converted into purified flue gas 13 which flows out from the top of the absorption tower 2 and is discharged into the atmosphere, and simultaneously analyzes the pre-purification flue gas 12 and purifies it.
  • the contents of sulfur dioxide and/or nitrogen oxides, carbon dioxide and oxygen in the post-flue gas 13 are A 1 and A 2 .
  • the hot lean liquid 14 is subjected to heat exchange, the temperature is raised, and then heated by the heat medium 21 to 90 ° C or higher through the rich liquid heater 9, and the rich liquid 15 having a temperature greater than 90 ° C enters the regeneration tower 10 from the upper end while
  • the stripping steam 17 enters the regeneration tower 10 from the bottom, and the rich liquid 15 having a temperature of more than 90 ° C in the regeneration tower 10 is in direct contact with the stripping steam 17 at this time, and sulfur dioxide and/or nitrogen oxides in the rich liquid 15 are at this time.
  • a small amount of carbon dioxide is analyzed and enters the stripping steam 17 to be mixed into the regenerated analytical gas 16 to flow out from the top of the regeneration tower 10, releasing sulfur dioxide and/or nitrogen oxides and a small amount of carbon dioxide at a temperature greater than 90 ° C.
  • the hot lean liquid 14 having a temperature greater than 90 ° C flows out from the bottom of the regeneration tower 10, and undergoes heat exchange through the tube of the heat exchanger 8 and the rich liquid 15 sent from the rich liquid pump 4 in the shell side, and the temperature is lowered.
  • the process is cooled to a normal temperature by the cooling water 20 of the shell side, and is sent to the lean liquid tank 5 by the lean liquid pump 6, and then the lean liquid 14 in the lean liquid tank 5 is pressurized by the desulfurization pump 3 and sent to the absorption tower. 2, the desulfurization and/or denitration is carried out.
  • the desulfurization and denitration solution is such that the lean liquid 14 absorbs sulfur dioxide and/or nitrogen oxides and a small amount of carbon dioxide in the absorption tower 2 and is converted into a rich liquid 15 which is in the regeneration tower 10
  • the heating, stripping and/or vacuum regeneration is again converted into a lean liquid 14, which is recycled and thus continuously circulated.
  • the regenerated analytical gas 16 flowing out from the top of the regeneration column 10 enters the concentration column 11 from the center, is in contact with the distilled water condensed at the upper end of the concentration column 11, and the water vapor in the regeneration analysis gas 16 is condensed in the condensation section of the concentration column 11.
  • the cooling water 20 is condensed, and concentrated sulfur dioxide and/or nitrogen oxide gas 18 composed of a mixture of non-condensed sulfur dioxide and/or nitrogen oxides and a small amount of carbon dioxide flows out of the concentration tower 11 and can be recovered as a raw material gas.
  • the condensed distilled water contains sulfur dioxide and/or nitrogen oxides, and continues to flow to the bottom of the concentration tower 11 to be in contact with the stripping steam 17 at the bottom.
  • the sulfur dioxide and/or nitrogen oxides in the distilled water are The gas stripping gas is analyzed by gas stripping, so that the condensed water is substantially free of gases such as sulfur dioxide and/or nitrogen oxides, and reaches the standard of condensed hot water for recycling, which can be recycled.
  • Absorption tower 2 Specification is ⁇ 219 ⁇ 4, total height is 7.2 meters, 4 layers of packing, 1 meter high per layer, material 316L stainless steel;
  • Lean liquid tank 5 the specification is ⁇ 450 ⁇ 3, the total height is 2.0 meters, and the material is 316L stainless steel;
  • Cooler 7 ⁇ 159 ⁇ 3, tube ⁇ 10 ⁇ 1, length 1.5 m, total heat exchange area 3.9 m 2 , material 316L stainless steel;
  • Rich liquid heater 9 ⁇ 159 ⁇ 3, tube ⁇ 32 ⁇ 1, length 0.9 m, total heat exchange area of 1.63 m 2 , material titanium;
  • Regeneration tower 10 the specification 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;
  • Concentration tower 11 The specification is ⁇ 159 ⁇ 4, the total height is 6.2 meters, the upper end is the titanium tube condenser, and the middle layer is 1.5 times higher. Meter, the lower layer of packing is 2.0 meters high and made of 316L stainless steel.
  • Booster fan 1 Model 2HB710-AH37, air supply volume 318m 3 /hr, wind pressure -290 ⁇ 390mbar (-29kPa ⁇ 39kPa), Shanghai Liwei Mechanical and Electrical Equipment 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 gas components analyzed by the inlet and outlet gases of the absorption tower 2 and the concentration tower 11 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 lean liquid 14, the rich liquid 15 and the condensed hot water 19 is analyzed by a chemical method, wherein the content of SO 2 in the solution is analyzed by iodometric method, and the solution is analyzed by the ruthenium chloride method.
  • the content of CO 2 was analyzed by the colorimetric method using naphthylethylenediamine hydrochloride colorimetric method, and the pH value of the solution was measured by a potential pH meter.
  • the gas was gasified with air, SO 2 , NO/NO 2 and CO 2 , and the gas components were recorded in the data of each experimental step.
  • Solution 1 The content of desulfurization and denitration agent synthesized by mixing ethylene glycol, citric acid and potassium hydroxide (1:1:1 molar ratio) is 15% (w/w), and ethylene glycol content is 75% (w/w). a desulfurization and denitration solution having a water content of 10% (w/w);
  • the synthesis method of the desulfurization and denitration agent is: firstly dissolving 48Kg of citric acid in 50Kg of distilled water, and then slowly adding 23.5Kg of potassium hydroxide to the citric acid aqueous solution, and slowly cooling, so that the temperature does not exceed 50 ° C, and dissolve thoroughly. Thereafter, a potassium citrate solution was formed, and 15.5 kg of ethylene glycol was added to the potassium citrate solution, and the mixture was uniformly stirred. The mixture was heated to 90 ° C to 120 ° C for 3 hours to obtain a reactant mixture of 137 Kg, wherein the desulfurization denitration agent was 78 Kg. Water 59Kg.
  • the present desulfurization and denitration solution is operated in the apparatus shown in Fig. 1 in the above-described embodiment, and the operating conditions are:
  • T 1 36 ⁇ 40.4°C
  • T 2 30.3 ⁇ 31.9°C
  • T 3 120.7 ⁇ 121.9°C
  • T 4 untested
  • T 5 untested
  • T 6 untested
  • F 1 40 m 3 /hr
  • F 2 0.232 m 3 / hr
  • F 3 not measured
  • F 4 not measured.
  • the experimental operation is as follows: Take the operation data of the white shift on April 12, 2014 as follows:
  • the desulfurization efficiency is 95.6% to 98.24%.
  • Regenerated release gas component A 3 SO 2 : not measured, NO X : not tested,
  • Condensed hot water component A 6 SO 2 : not measured.
  • Solution 2 The content of the desulfurization denitration agent synthesized by mixing polyethylene glycol 400, citric acid and potassium hydroxide (1:1:1:1 molar ratio) is 15% (w/w), and the ethylene glycol content is 75% (w/ w) a desulfurization and denitration solution having a water content of 10% (w/w);
  • the synthesis method of the desulfurization and denitration agent is: firstly dissolving 24Kg of citric acid in 50Kg of distilled water, and then slowly adding 11.75Kg of potassium hydroxide to the citric acid aqueous solution, and slowly cooling, so that the temperature does not exceed 50 ° C, completely dissolved. After that, a potassium citrate solution was formed, and 50Kg of polyethylene glycol 400 was added to the potassium citrate solution, and the mixture was stirred uniformly, and heated to 90 ° C to 120 ° C for 3 hours to obtain a reactant mixture of 135.75 Kg, wherein the desulfurization and denitration agent was 81.25Kg, water 54.5Kg.
  • the present desulfurization and denitration solution is operated in the apparatus shown in Fig. 1 in the above-described embodiment, and the operating conditions are:
  • T 1 31.4 to 35.8 ° C
  • T 2 33.6 to 38.7 ° C
  • T 3 92.6 to 107.9 ° C
  • T 4 89.7 to 115.5 ° C
  • T 5 89.8 to 100.2 ° C
  • T 6 29.6 to 46.1 ° C;
  • F 1 95m 3 / hr
  • F 2 0.238m 3 / hr
  • F 3 3.5 ⁇ 24.9m 3 / hr
  • F 4 3.8 ⁇ 11.4m 3 / hr.
  • the experimental operation was carried out according to the implementation method.
  • the operation data of the night shift on May 13, 2014 was as follows:
  • Treated gas component A 2 SO 2: 5.8 ⁇ 10.9ppm, NO X: not determined,
  • the desulfurization efficiency is: 98.49% to 99.46%.
  • Regenerated release gas component A 3 SO 2 : 79.98% (v/v), NO X : not detected,
  • Solution 3 The content of desulfurization and denitration agent synthesized by mixing ethylene glycol, citric acid and N-methyldiethanolamine (MDEA) (1:1:1 molar ratio) is 15% (w/w), polyethylene glycol 200 a desulfurization and denitration solution having a composition of 75% (w/w) and a water content of 10% (w/w);
  • MDEA N-methyldiethanolamine
  • the synthesis method of the desulfurization and denitration agent is: firstly dissolving 48Kg of citric acid in 50Kg of distilled water, and then slowly adding 29.75Kg of N-methyldiethanolamine (MDEA) to the aqueous solution of citric acid, and slowly cooling, so that the temperature is not After more than 50 ° C, after dissolution, a solution of citric acid MDEA was formed, and then 15.5 Kg of ethylene glycol was added to the citric acid MDEA solution, and the mixture was stirred uniformly, and heated to 90 ° C to 120 ° C for 3 hours to obtain a reactant mixture of 143.25 Kg.
  • the desulfurization and denitration agent is 88.75 Kg and the water is 54.5 Kg.
  • the present desulfurization and denitration solution is operated in the apparatus shown in Fig. 1 in the above-described embodiment, and the operating conditions are:
  • T 1 30.6 to 36.5 ° C
  • T 2 21.6 to 28.2 ° C
  • T 3 125 to 127.1 ° C
  • T 4 123.8 to 127.1 ° C
  • T 5 103 to 118 ° C
  • T 6 27.8 to 29.9 ° C;
  • P 1 6.4 to 7 kPa
  • P 2 2.6 to 2.85 kPa
  • P 3 3.5 to 4.45 kPa
  • P 5 0.95 to 1.55 kPa
  • F 1 164 m 3 /hr
  • F 2 0.125 m 3 / hr
  • F 3 19.7 to 20.2 m 3 /hr
  • F 4 0 to 4.2 m 3 /hr.
  • the experimental operation is as follows: Take the operation data of the evening shift on January 7, 2015 as follows:
  • the desulfurization efficiency is: 99.39% to 99.58%.
  • Regenerated release gas component A 3 SO 2 : 89.9% to 90.1% (v/v), NO X : 0.1% (v/v),
  • Solution 4 The content of desulfurization and denitration agent synthesized by mixing polyethylene glycol 200, citric acid and N-methyldiethanolamine (MDEA) (1:1:1 molar ratio) is 15% (w/w), polyethylene A desulfurization and denitration solution having an alcohol content of 75% (w/w) and a water content of 10% (w/w).
  • MDEA N-methyldiethanolamine
  • the synthesis method of the desulfurization and denitration agent is: firstly dissolving 48Kg of citric acid in 50Kg of distilled water, and then slowly adding 29.75Kg of N-methyldiethanolamine (MDEA) to the aqueous solution of citric acid, and slowly cooling, so that the temperature is not After more than 50 ° C, after dissolution, a solution of citric acid MDEA was formed, and 50 kg of polyethylene glycol 200 was added to the citric acid MDEA solution, and the mixture was stirred uniformly, and heated to 90 ° C to 120 ° C for 3 hours to obtain a reactant mixture of 177.75 Kg.
  • the desulfurization and denitration agent is 173.25 Kg and the water is 54.5 Kg.
  • the present desulfurization and denitration solution is operated in the apparatus shown in Fig. 1 in the above-described embodiment, and the operating conditions are:
  • T 1 28.6 to 31.8 ° C
  • T 2 25.7 to 27 ° C
  • T 3 120.5 to 121.7 ° C
  • T 4 112.9 to 113.7 ° C
  • T 5 105 to 105.5 ° C
  • T 6 67.3 to 73.4 ° C;
  • P 1 8.89 to 9 kPa
  • P 2 1.95 to 2.15 kPa
  • P 3 2.15 to 3.1 kPa
  • P 5 1.75 to 2.35 kPa
  • F 1 140 m 3 /hr
  • F 2 0.202 m 3 / hr
  • F 3 19.7 to 20.2 m 3 /hr
  • F 4 0 to 4.2 m 3 /hr.
  • the operation data of the evening shift on February 11, 2015 is as follows:
  • Treated gas component A 2 SO 2: 4 ⁇ 14.5ppm, NO X: 0 ⁇ 0.1ppm,
  • the desulfurization efficiency is: 99.44% to 99.65%; the denitration efficiency is 100%.
  • Regenerated release gas component A 3 SO 2 : 89.9% to 90.1% (v/v), NO X : 0 to 0.1% (v/v),
  • the desulfurization and denitration agent of the present invention has a good effect and can be used for removing sulfur dioxide and nitrogen oxides in a gas in actual industrialization.

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Abstract

一种脱硫脱硝剂，由多醇和/或聚多醇类物质、多元羧酸类物质和碱性物质混合，加热到90℃以上，经缩合和/或聚合后得到的大分子或高分子的醚类和/或酯类物质，用于脱除气体中的二氧化硫和/或氮氧化物。

Description

一种脱硫脱硝剂 技术领域
本发明涉及气体脱硫和/或脱硝工业领域，具体涉及一种烟道气或各种燃烧尾(废)气脱硫和/或脱硝的脱硫脱硝剂。
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。所以，烟道气脱硫和脱硝的研究相当迫切，也具有挑战性。
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。
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。
湿法脱硫工艺所用的脱硫剂主要是碳酸钙、碳酸镁、氧化钙、氧化镁、氨、亚硫酸钠(或钾)和有机酸—有机酸盐缓冲溶液等。
其脱硫工艺是将碳酸钙、碳酸镁、氧化钙和氧化镁等磨成目数大于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；该浆液在吸收塔中与烟道气接触，气体中二氧化硫和浆液中的碳酸钙、或碳酸镁、或氧化钙、或氧化镁反应生成亚硫酸钙或亚硫酸镁。
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；硫酸钙浆液流出吸收塔，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。
而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浆液，循环使用；分离出的亚硫酸镁在1235K以上煅烧，生成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，由于碳酸钙、碳酸镁、氧化钙和氧化镁等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。
氨法脱硫工艺是以氨作为脱硫剂，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。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，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。
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，尤其是碳酸盐作为脱硫剂，这些脱硫剂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)法是以亚硫酸钠(或钾)脱硫剂，用其水溶液在吸收塔中与烟道气接触，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)溶液经加热再生，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。该法构思比较好，但是实际试验表明亚硫酸氢钠(或钾)溶液加热再生率非常低，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。所以该法一直无法实现工业化。
韦尔曼—洛德(Wellman-Lord)法脱硫实际上就是改进的亚硫酸钠循环法，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是用有机酸和有机酸盐组成的缓冲溶液作为脱硫液，在吸收塔中与烟道气接触，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；该溶液经加热再生，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。该法构思比较好，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，所以该法一直无法实现工业化。在该法的基础上，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主要有选择性催化还原法(SCR)或选择性非催化还原法(SNCR)。
选择性催化还原方法(SCR)是利用催化床或系统对烟道气流进行处理，是将氨或脲注入烟道气中混合，混合以后经过催化剂层，选择性地将NOX转化(还原)为N2和H2O。SCR法是目前最为成熟的脱硝效率最高的脱硝技术。1975年在日本Shimoneski电厂建立了第一个SCR系统的示范工程，其后SCR技术在日本得到了广泛应用。在欧洲已有120多台大型装置的成功应用经验，其NOX的脱除率可达到80％～90％。到目前为止，日本大约有170套装置， 接近100GW容量的电厂安装了这种设备，美国政府也将SCR技术作为主要的电厂控制NOX的主要技术，报道指出SCR方法已成为目前国内外电厂脱硝比较成熟的主流技术。
SCR法烟气脱硝原理是在以TiO2、V2O5为主要成分的催化剂催化下，在温度为280～400℃时，或在以TiO2、V2O5、MnO为主要成分的催化剂催化下，在大于180℃时，向烟气中喷入氨，将NO和NO2还原成N2和H2O来达到脱硝的目的。
SNCR脱硝技术是选择性非催化还原(Selective Non-Catalytic Reduction)技术，是一种不用催化剂，在850～1100℃的温度范围内，将含氨基的还原剂(如氨水，尿素溶液等)喷入炉内，将烟气中的NO和NO2还原成N2和H2O来达到脱硝的目的。但工业SNCR系统的NOX去除率仅为30-70％。
SCR和SNCR脱硝工艺氨消耗量都较大，由于烟道气中含有约4％～9％的O2，氨气或含氨基的尿素和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。
现有SCR和SNCR脱除烟气中NO的方法还存在一些缺陷。对于以氨为还原剂的脱NO方法，一般是以氨和尿素或尿素水溶液作为还原剂的来源，如果注入的氨或尿素量过多，将导致所谓的氨穿透，排放出来的氨比排放的NOx更有害，过多的氨用量经过氧化可能导致NOx的生成，而且还原剂氨运输、储存过程中安全环保的要求很高。另外，脱硝过程中所用的催化剂会受到高浓度烟尘的冲刷、磨损和飞灰中杂质的污染，烟气温度过高还会使催化剂发生烧结、失活，SO2存在会导致催化剂活性的快速下降。
SCR和SNCR脱硝法氨消耗量较大，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。
国内外许多研究者利用臭氧同时将烟气中的SO2和NO氧化成SO3和NO2，然后用石灰/石灰石、氢氧化钠等吸收，达到同时脱除SO2和NO的作用。但是由于产生臭氧的装置非常昂贵，投资极大；且臭氧生产成本非常高，将1摩尔SO2或1摩尔NO氧化成SO3和NO2，分别需要消耗1.5～3摩尔的臭氧，生产1公斤臭氧分别需要消耗约10度电和10～20公斤纯氧；能耗大，消耗高，投资大，使得臭氧烟道气脱硫脱硝技术现在无法实现大规模工业化。
CN101352645A公开了一种催化氧化脱硝工艺，以TiO2或ZrO2-TiO2为载体，Co为活性 组分的催化剂，利用烟气中自身含有的氧气，将NO氧化成易溶于水的NO2后，利用碱液吸收，将氮氧化物脱除。
CN1768902A公开了一种锅炉烟气脱硝方法，在温度范围为110～150℃的锅炉烟道低温段喷入臭氧O3，将锅炉烟气中一氧化氮NO氧化成为易溶于水的高价态氮氧化物NO2、NO3或N2O5，喷入的臭氧O3与锅炉烟气中的NO的摩尔比为0.5～1.5，然后使用碱液水洗涤来脱除烟气中的氮氧化物。但是，该技术实际使用中脱硝效率较低，臭氧消耗极高，要达到排放标准时，其运行费用特别高，企业无法承受，所以该技术一直无法实现大规模工业化。
发明内容
本发明提供了一种烟道气脱硫脱硝剂，其是由多醇和/或聚多醇类物质、多元羧酸类物质和碱性物质共同混合，加热到90℃以上的条件下聚合而成的物质。所述多醇和/或聚多醇类物质、多元羧酸类物质和碱性物质混合经缩合和/或聚合后，羟基与羟基或羟基与羧基会缩合失去一个水分子后而形成大分子或高分子的醚类和/或酯类物质，同时分子中的羧基还会和碱性物质进一步结合。
其中，所述的多醇是指分子中含有二个或二个以上羟基基团的有机化合物(含酚类)，如乙二醇、丙二醇、1，2，3-丙三醇(甘油)、1，2(或1，3或1，4或2，3)-丁二醇、1，4-丁烯二醇、戊二醇、新异戊二醇、异戊二醇、1，5-戊二醇、1，6-己二醇、苯二酚、1，2，4-丁三醇、异丁三醇、戊三醇、异戊三醇、苯三酚、季戊四醇、戊四醇、异戊四醇、丁四醇、没食子酸、单宁等。
所述的聚多醇类物质是高分子或大分子的物质，是一个多醇分子中的羟基与另一个多醇分子中的羟基缩合失去一个水分子而形成醚键，这种以醚键的方式连接的分子就叫聚多醇类物质，如聚乙二醇、聚丙二醇、聚丁二醇、聚丙醇和聚丁醇、聚乙二醇一甲醚、聚乙二醇二甲醚、聚乙二醇一乙醚、聚乙二醇二乙醚等。
所述的多元羧酸类物质是在同一分子中至少含有两个或两个以上羧基的化合物，如乙二酸、丙二酸、丁二酸、氨基乙二酸、氨三乙酸、EDTA、酒石酸、鞣质酸、多聚没食子酸和柠檬酸等。
所述的碱性物质包含无机碱性物质和/或有机碱性物质。所述的无机碱性物质包括碱金属、碱土金属或过渡金属的氢氧化物、碳酸盐、羧酸盐、络合物，以及氨；优选含有Li、Na、K、Mg或Ca的氢氧化物、碳酸盐。所述的有机碱性物质主要为有机胺类物质，有机胺选自 脂肪胺、芳香族胺和醇胺类，如脂肪胺选自：甲胺、二甲胺、三甲胺、一乙胺、二乙胺、三乙胺、一丙胺、二丙胺、三丙胺、正丙胺、异丙胺、一丁胺、二丁胺、三丁胺、正丁胺、仲丁胺、异丁胺、叔丁胺、乙二胺、丙二胺、己二胺、三亚乙基二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、多亚乙基多胺、环戊胺、环己胺、环庚胺；芳香族胺选自：苯胺、N-甲基苯胺、N-乙基苯胺、N-丙基苯胺、N-丁等基苯胺、N,N-二甲基苯胺、N,N-二乙基苯胺、N,N-二丙基苯胺、N,N-二丁基苯胺、苯二胺、α-萘胺、卤代苯胺、硝基苯胺、磺酸基苯胺；醇胺类选自：一甲醇胺、二甲醇胺、三甲醇胺、一乙醇胺、二乙醇胺、三乙醇胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N,N-二异丙基乙醇胺、N-甲基二乙醇胺(MDEA)、一丙醇胺、二丙醇胺、三丙醇胺、异丙醇胺、二异丙醇胺、三异丙醇胺、一丁醇胺、二丁醇胺、三丁醇胺、N-羟乙基乙二胺、N,N’-二羟乙基乙二胺、N,N-二羟乙基苯胺、N-乙基-N-羟乙基苯胺、N-甲基-N-羟乙基苯胺、邻氨基苯酚、间氨基苯酚、对氨基苯酚、2,4,6-三(二甲氨基甲基)酚、3-二乙胺基苯酚、2-氨基-5硝基苯酚、氨噻肟酸、N-甲基吡咯烷醇、2,4-二氨基-6-羟基嘧啶、三聚氰酸、2-(2’-羟基-5’-甲基苯基)苯并三唑、γ酸、J酸、苯基J酸、芝加哥酸及其盐、H酸及其盐、双J酸、猩红酸及其盐等。
所述的脱硫脱硝剂是由多醇和/或聚多醇类物质、多元羧酸类物质和碱性物质按一定比例混合，然后加热到90℃以上，经酯化和/或醚化反应以后所形成的一类大分子或高分子的醚类和/或酯类物质；其比例为：多醇和/或聚多醇类物质∶多元羧酸类物质∶碱性物质的摩尔比为：10∶0.5～2∶0.1～3，优选为1∶0.7～1∶0.3～2，更优选为1∶0.9～1.3∶0.5～1.5，极优选为1∶0.9～1.1∶0.5～1.2，最优选为1∶1∶0.5～1。
在乙二醇和/或聚乙二醇和/或水组成的溶液中加入本发明所述的脱硫脱硝剂，形成本发明的脱硫脱硝溶液，其中脱硫脱硝剂的用量为0.1-50wt％，优选2-30wt％，更优选5-25wt％，最优选10-20wt％。
经过深入的研究发现，在EG(乙二醇)和/或PEG(聚乙二醇)和/或水溶液中，本发明的脱硫脱硝剂所示的这类大分子或高分子的醚类和/或酯类物质对SOX和NOX(X为自然数)具有选择性的捕获能力；其具有选择性的捕获能力的结果是一种综合作用的结果，这些作用力是弱作用力，包括醚键作用力、酯键作用力、络合键作用力和缓冲溶液的作用力等。而且捕获在溶液中的SOX和NOX在气体(尤其是蒸汽)气提的条件下，很容易释放出来。
所述的脱硫脱硝溶液可以用于同时脱除废气中的SOX和NOX，也可以用于单独脱除废气中的SOX(包括SO2和SO3)，或用于单独脱除废气中的NOX(包括NO和NO2)。
为了更清晰地叙述本发明的物质结构和合成方法，下面仅以乙二醇、柠檬酸和氢氧化钠，聚乙二醇、柠檬酸和氢氧化钠，乙二醇、柠檬酸和N-甲基二乙醇胺(MDEA)，聚乙二醇、柠檬酸和N-甲基二乙醇胺(MDEA)四种反应配方为例，说明本发明的脱硫脱硝剂的合成方法。
乙二醇、柠檬酸和氢氧化钠的酯化过程如下：
Figure PCTCN2016075922-appb-000001
聚乙二醇、柠檬酸和氢氧化钠的酯化过程如下：
Figure PCTCN2016075922-appb-000002
乙二醇、柠檬酸和N-甲基二乙醇胺(MDEA)可发生如下的醚化和酯化的过程：
醚化和化合过程如下：
Figure PCTCN2016075922-appb-000003
酯化过程如下：
Figure PCTCN2016075922-appb-000004
此外，在不使用NaOH和硫酸的情况下，N-甲基二乙醇胺(MDEA)作为有机碱可替代上述的NaOH和柠檬酸反应，然后再和乙二醇发生醚化反应。
聚乙二醇、柠檬酸和N-甲基二乙醇胺(MDEA)可发生如下的醚化和酯化的过程：
醚化和化合过程如下：
Figure PCTCN2016075922-appb-000005
酯化过程如下：
Figure PCTCN2016075922-appb-000006
Figure PCTCN2016075922-appb-000007
以上所列举的合成配方并不是限定本发明的脱硫脱硝剂仅仅是用乙二醇和/或聚乙二醇、柠檬酸、氢氧化钠和/或MDEA来合成，而是用多醇和/或聚多醇类物质、多元羧酸类物质和碱性物质按一定比例混合，然后加热到90℃以上，经酯化和/或醚化反应以后所形成的一类大分子或高分子的醚类和/或酯类物质，碱性物质包括无机碱性物质和有机碱性物质。经酯化和/或醚化反应以后，液体的颜色由无色转变成黄褐色、粘稠状液体，沸点显著升高。
当用多醇和/或聚多醇类物质、多元羧酸类物质和无机碱性物质为合成原料时，其反应过程是多醇和/或聚多醇类物质与含羟基的多元羧酸和/或多元羧酸类物质中的羟基或羧基缩合失去一个水分子后缩合来合成大分子或高分子的醚类和/或酯类的脱硫脱硝剂物质，这类脱硫脱硝剂分子中的一个羧基和无机碱性物质的阳离子结合(该阳离子可以是氢离子、铵离子、钠离子、钾离子、过渡金属离子等任意阳离子)。以上所述的多醇是指分子中含有二个或二个以上羟基基团的有机化合物(含酚类)，如乙二醇、丙二醇、1，2，3-丙三醇(甘油)、(1，2或1，3或1，4或2，3)-丁二醇、1，4-丁烯二醇、新异戊二醇、季戊四醇、1，5-戊二醇、1、6-己二醇、1，2，4-丁三醇、丁四醇、二乙二醇二醚、苯二酚、苯三酚、没食子酸和单宁等；所述的聚多醇类物质是高分子或大分子的物质，是一个多醇分子中的羟基与另一个多醇分子中的羟基缩合失去一个水分子而形成醚键，这种以醚键的方式连接的分子就是聚多醇类物质，如聚乙二醇、聚丙二醇、聚丁二醇等；所述的含羟基的多元羧酸是在同一分子中至少含有一个羟基和含有两个或两个以上的羧基化合物，如鞣质酸、多聚没食子酸、柠檬酸、羟基脂肪多酸、羟基对苯二甲酸、羟基邻苯二甲酸、羟基间苯二甲酸、羟基苯三甲酸、多羟基苯三甲酸及其它羟基芳香烃多酸和多羟基芳香烃多酸；所述的多元羧酸类物质是在同一分子中至少含有两个或两个以上的羧基化合物，如EDTA、乙二酸、丙二酸、丁二酸、氨基乙二酸、氨三乙酸、脂肪多酸、对苯二甲酸、邻苯二甲酸、间苯二甲酸、均苯三甲酸及其它芳香烃多酸。
当用多醇和/或聚多醇类物质、多元羧酸类物质和有机碱性物质为合成原料时，其反应过程是多醇和/或聚多醇类物质与含羟基的多元羧酸和/或多元羧酸类物质中的羟基或羧基缩合失去一个水分子后缩合来合成大分子或高分子的醚类和/或酯类的脱硫脱硝剂物质，这类脱硫 脱硝剂分子中的一个羧基和有机碱性物质以有机阳离子形式结合，当有机碱性物质中含有羟基时，该羟基还会和大分子或高分子的醚类和/或酯类物质中的羧基发生酯化反应，形成酯类物质。所述的有机碱性物质是有机胺类物质，有机胺选自脂肪胺、芳香族胺和醇胺类。所述脂肪胺选自：甲胺、二甲胺、三甲胺、一乙胺、二乙胺、三乙胺、一丙胺、二丙胺、三丙胺、正丙胺、异丙胺、一丁胺、二丁胺、三丁胺、正丁胺、仲丁胺、异丁胺、叔丁胺、乙二胺、丙二胺、己二胺、三亚乙基二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、多亚乙基多胺、环戊胺、环己胺、环庚胺；芳香族胺选自：苯胺、N-甲基苯胺、N-乙基苯胺、N-丙基苯胺、N-丁等基苯胺、N,N-二甲基苯胺、N,N-二乙基苯胺、N,N-二丙基苯胺、N,N-二丁基苯胺、苯二胺、α-萘胺、卤代苯胺、硝基苯胺、磺酸基苯胺；醇胺类选自：一甲醇胺、二甲醇胺、三甲醇胺、一乙醇胺、二乙醇胺、三乙醇胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N,N-二异丙基乙醇胺、N-甲基二乙醇胺(MDEA)、一丙醇胺、二丙醇胺、三丙醇胺、异丙醇胺、二异丙醇胺、三异丙醇胺、一丁醇胺、二丁醇胺、三丁醇胺、N-羟乙基乙二胺、N,N’-二羟乙基乙二胺、N,N-二羟乙基苯胺、N-乙基-N-羟乙基苯胺、N-甲基-N-羟乙基苯胺、邻氨基苯酚、间氨基苯酚、对氨基苯酚、2,4,6-三(二甲氨基甲基)酚、3-二乙胺基苯酚、2-氨基-5硝基苯酚、氨噻肟酸、N-甲基吡咯烷醇、2,4-二氨基-6-羟基嘧啶、三聚氰酸、2-(2’-羟基-5’-甲基苯基)苯并三唑、γ酸、J酸、苯基J酸、芝加哥酸及其盐、H酸及其盐、双J酸、猩红酸及其盐等。
本发明脱硫脱硝剂与传统的脱硫和/或脱硝剂(如碳酸钙、氧化钙、氨和/或尿素、金属氧化物等)相比，具有如下优点：①传统的脱硫和/或脱硝剂与二氧化硫或氮氧化物发生不可逆反应，其副产物是硫酸钙和亚硫酸钙，或硫酸铵和亚硫酸铵，氮气和水，本发明的烟道气脱硫脱硝剂与二氧化硫和/或氮氧化物发生弱结合的可逆反应，气提再生后，脱硫脱硝剂恢复原来结构，并释放出二氧化硫和/或氮氧化物，并副产物是高纯度的二氧化硫和/或氮氧化物(或硝酸盐)，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剂是高沸点、无 毒、无害的安全性很高的醚类和/或酯类高分子化合物，化学稳定性强，沸点高，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传统的湿法脱硫剂是碳酸钙或氧化钙，需要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剂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传统的脱硫剂或脱硝剂是一次性使用，所以运行费用高，且无法产生经济效益，本发明的烟道气脱硫脱硝剂运行费用低，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传统的湿法脱硫和/或脱硝剂适合用于较低硫含量或低氮氧化物含量的气体脱硫和/或脱硝，本发明的烟道气脱硫脱硝剂既可以用于低硫含量和/或低氮氧化物含量气体的脱硫和/或脱硝，也可以用于高硫含量和/或高氮氧化物含量气体的脱硫和/或脱硝。同时，本发明的烟道气脱硫脱硝剂的脱硫脱硝的净化度高，可以将气体中的总硫和氮氧化物的含量稳定地降至30mg/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，操作简单。
本发明的烟道气脱硫脱硝剂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和/或脱硝，上述含硫和/或含氮氧化物的气体中的总硫和/或总氮氧化物的含量均小于99.9％(体积比)。
为了验证本发明的脱硫脱硝剂是否可行，我们设计了图1所示的模拟烟道气脱硫脱硝工艺流程和设备。并用本发明的脱硫脱硝剂分别溶解在乙二醇或聚乙二醇中组成脱硫脱硝溶液，在图1所示的工艺流程和设备中进行脱硫和/或脱硫实验。具体实验方式在具体实施方式中进行了描述。
附图说明
图1是模拟烟道气脱硫脱硝工艺流程和设备的示意图。
图1中：1是增压风机，2是吸收塔，3是脱硫泵，4是富液泵，5是贫液槽，6是贫液泵，7是冷却器，8是热交换器，9是富液加热器，10是再生塔，11是提浓塔，12是净化前烟道气，13是净化后烟道气，14是贫液，15是富液，16是再生解析气，17是气提用蒸汽，18是浓缩的二氧化硫和/或氮氧化物气体，19是冷凝热水，20是冷却水，21是加热介质。图中用圆圈圈起来的各符号所代表的意义：F1、F2、F3、F4分别表示净化前烟道气12的流量、脱硫贫液14的流量、进再生塔10的蒸汽流量、进提浓塔11的蒸汽流量；A1为净化前烟道气12的组成、A2为净化后烟道气13的组成、A3为浓缩的二氧化硫和/或氮氧化物气体18的组成、A4为富液15中的SO2和NO含量(包括pH值)、A5为贫液14中的SO2和NO的含量(包括pH值)、A6为冷凝热水19中的SO2和NO含量；P1为吸收塔2底部压力、P2为吸收塔2顶部压力、P3为再生塔10中压力、P4为气提用蒸汽17的压力、P5为提浓塔11中的压力；T1为吸收塔2底部的温度、T2为吸收塔2顶部的温度、T3为再生塔10中的温度、T4为气提用蒸汽17的温度、T5为提浓塔11中的温度、T6为浓缩的二氧化硫和/或氮氧化物气体18的温度。
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脱硫脱硝剂的实际净化效果。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：
首先将本发明的脱硫脱硝剂溶解在乙二醇或聚乙二醇中形成脱硫脱硝溶液(贫液14)，注入贫液槽5中，开启所有设备进行运行。运行方式如下：
如图1所示：温度低于80℃(最佳温度为35℃以下)的净化前烟道气12经增压风机1增压后从底部进入吸收塔2，同时，贫液14从顶部进入吸收塔2，在吸收塔2中，净化前烟道气12和贫液14直接接触，此时净化前烟道气12中的二氧化硫和/或氮氧化物和少量二氧化碳被贫液14吸收，被吸收了二氧化硫和/或氮氧化物及少量二氧化碳的净化前烟道气12转变成净化后烟道气13从吸收塔2顶部流出，排入大气中，同时在线分析净化前烟道气12和净化后烟道气13中的二氧化硫和/或氮氧化物、二氧化碳和氧气的含量A1和A2。吸收了二氧化硫和/或氮氧化物及少量二氧化碳的贫液14转变成富液15，从吸收塔2的底部流出，经富液泵4增压，又经热交换器8的壳程与再生塔10来的热的贫液14进行热交换，温度升高， 然后再经过富液加热器9被热介质21加热至90℃以上，温度大于90℃的富液15从上端进入再生塔10中，同时气提用蒸汽17从底部进入再生塔10中，在再生塔10中温度大于90℃的富液15与气提用蒸汽17进行直接接触，此时富液15中的二氧化硫和/或氮氧化物及少量二氧化碳解析出来，并进入气提用蒸汽17中混合成再生解析气16从再生塔10的顶部流出，释放了二氧化硫和/或氮氧化物及少量二氧化碳的温度大于90℃的富液15转变成温度大于90℃的热的贫液14，从再生塔10底部流出，经过热交换器8的管程与壳程中的由富液泵4送来的富液15进行热交换，温度降低，降低了温度的贫液14走冷却器7的管程，被壳程的冷却水20冷却至常温，并由贫液泵6增压送至贫液槽5中，然后贫液槽5中的贫液14由脱硫泵3增压又送至吸收塔2中进行脱硫和/或脱硝作用，脱硫脱硝溶液就是这样由贫液14在吸收塔2中吸收二氧化硫和/或氮氧化物及少量二氧化碳后转变成富液15，富液15在再生塔10中被加热、气提和/或真空再生又转变成贫液14，贫液14又循环使用，如此连续循环。从再生塔10的顶部流出的再生解析气16从中部进入提浓塔11中，与提浓塔11上端冷凝下来的蒸馏水接触，再生解析气16中的水蒸汽在提浓塔11的冷凝段被冷却水20冷凝下来，不冷凝的二氧化硫和/或氮氧化物及少量二氧化碳等混合气体组成的浓缩的二氧化硫和/或氮氧化物气体18从提浓塔11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和/或氮氧化物等物质，继续流到提浓塔11的底部，与底部来的气提用蒸汽17接触，蒸馏水中的二氧化硫和/或氮氧化物等气体被气提用蒸汽17气提解析出来，使冷凝水中基本不含二氧化硫和/或氮氧化物等气体，达到回收用的冷凝热水19标准，可以回收使用。
图1所示的模拟烟道气脱硫脱硝工艺流程和设备中的各种设备的规格如下：
吸收塔2：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5：规格为φ450×3，总高2.0米，材质316L不锈钢；
冷却器7：φ159×3，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8：φ159×3，2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9：φ159×3，列管φ32×1，长0.9米，总换热面积为1.63m2，材质钛材；
再生塔10：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11：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1：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；
富液泵4、脱硫泵3和贫液泵6：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；
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；
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2进、出口气体和提浓塔11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。
用化学方法对贫液14、富液15和冷凝热水19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，用电位pH值计测定溶液的pH值。
用空气、SO2、NO/NO2和CO2进行配气，气体成分见各实验步骤的数据记录。
根据本发明的脱硫脱硝剂，我们配置了如下四种脱硫脱硝溶液进行实验，试验结果如下：
溶液1：由乙二醇、柠檬酸和氢氧化钾(1∶1∶1摩尔比)混合合成的脱硫脱硝剂含量为15％(w/w)、乙二醇含量75％(w/w)、水含量10％(w/w)组成的脱硫脱硝溶液；
本脱硫脱硝剂的合成方法是：先将柠檬酸48Kg溶解在50Kg蒸馏水中，然后再向柠檬酸水溶液中慢慢加入23.5Kg氢氧化钾，同时慢慢冷却，使温度不超过50℃，溶解彻底以后，形成了柠檬酸钾溶液，再向柠檬酸钾溶液中加入15.5Kg乙二醇，搅拌均匀，加热至90℃～120℃反应3小时，获得反应物混合物137Kg，其中脱硫脱硝剂为78Kg，水59Kg。然后减压蒸发 掉7Kg水，剩余130Kg脱硫脱硝剂水溶液，其中，脱硫脱硝剂为78Kg，水52Kg。然后再向该130Kg脱硫脱硝剂水溶液中加入390Kg乙二醇，搅拌、混和，得脱硫脱硝剂含量为15％(w/w)、乙二醇含量为75％(w/w)、水含量为10％(w/w)的脱硫脱硝溶液520Kg。用该脱硫脱硝溶液进行如下试验：
用本脱硫脱硝溶液在图1所示的装置中按以上所述的实施方式运行，运行条件是：
T1＝36～40.4℃，T2＝30.3～31.9℃，T3＝120.7～121.9℃，T4＝未测，T5＝未测，T6＝未测；
P1＝6.65kPa，P2＝未测，P3＝0kPa，P5＝0kPa；
F1＝40m3/hr，F2＝0.232m3/hr，F3＝未测，F4＝未测。
按照实施方法进行实验运行，取2014年4月12日白班的运行数据如下：
处理前气体成分A1：SO2：690～838ppm，    NOX：未测，
                  CO2：未测，           O2：未测。
处理后气体成分A2：SO2：12.3～37ppm，    NOX：未测，
                  CO2：未测，           O2：未测。
          脱硫效率为：95.6％～98.24％。
再生释放气体成分A3：SO2：未测，         NOX：未测，
                    CO2：未测，         O2：未测。
富液成分A4：SO2：0.81～1.06g/L，        NOX：未测，
            pH：2.56～2.75。
贫液成分A5：SO2：0.51～0.89g/L，        NOX：未测，
            pH：2.9～3.45。
冷凝热水成分A6：SO2：未测。
溶液2：由聚乙二醇400、柠檬酸和氢氧化钾(1∶1∶1摩尔比)混合合成的脱硫脱硝剂含量为15％(w/w)、乙二醇含量75％(w/w)、水含量10％(w/w)组成的脱硫脱硝溶液；
本脱硫脱硝剂的合成方法是：先将柠檬酸24Kg溶解在50Kg蒸馏水中，然后再向柠檬酸水溶液中慢慢加入11.75Kg氢氧化钾，同时慢慢冷却，使温度不超过50℃，溶解彻底以后，形成了柠檬酸钾溶液，再向柠檬酸钾溶液中加入50Kg聚乙二醇400，搅拌均匀，加热至90℃～120℃反应3小时，获得反应物混合物135.75Kg，其中脱硫脱硝剂为81.25Kg，水54.5Kg。然后再向该135.75Kg脱硫脱硝剂水溶液中加入404.25Kg聚乙二醇400，搅拌、混和，得脱 硫脱硝剂含量为15％(w/w)、聚乙二醇含量为40075％(w/w)、水含量为10％(w/w)的脱硫脱硝溶液540Kg。用该脱硫脱硝溶液进行如下试验：
用本脱硫脱硝溶液在图1所示的装置中按以上所述的实施方式运行，运行条件是：
T1＝31.4～35.8℃，T2＝33.6～38.7℃，T3＝92.6～107.9℃，T4＝89.7～115.5℃，T5＝89.8～100.2℃，T6＝29.6～46.1℃；
P1＝未测，P2＝未测，P3＝未测，P5＝未测；
F1＝95m3/hr，F2＝0.238m3/hr，F3＝3.5～24.9m3/hr，F4＝3.8～11.4m3/hr。
按照实施方法进行实验运行，取2014年5月13日夜班的运行数据如下：
处理前气体成分A1：SO2：683.2～1083.7ppm，     NOX：未测，
                  CO2：3.14～3.78％(v/v)，    O2：未测。
处理后气体成分A2：SO2：5.8～10.9ppm，         NOX：未测，
                  CO2：3.27～3.92％(v/v)，    O2：未测。
        脱硫效率为：98.49％～99.46％。
再生释放气体成分A3：SO2：79.98％(v/v)，       NOX：未测，
                    CO2：未测，               O2：未测。
富液成分A4：SO2：1.2233～1.9282g/L，          NOX：未测，
            pH：3.65～3.92。
贫液成分A5：SO2：0.0622～0.2281g/L，          NOX：未测，
            pH：3.94～4.02。
冷凝热水成分A6：SO2：0.0019～0.0031g/L。
溶液3：由乙二醇、柠檬酸和N-甲基二乙醇胺(MDEA)(1∶1∶1摩尔比)混合合成的脱硫脱硝剂含量为15％(w/w)、聚乙二醇200含量75％(w/w)、水含量10％(w/w)组成的脱硫脱硝溶液；
本脱硫脱硝剂的合成方法是：先将柠檬酸48Kg溶解在50Kg蒸馏水中，然后再向柠檬酸水溶液中慢慢加入29.75Kg N-甲基二乙醇胺(MDEA)，同时慢慢冷却，使温度不超过50℃，溶解彻底以后，形成了柠檬酸MDEA溶液，再向柠檬酸MDEA溶液中加入15.5Kg乙二醇，搅拌均匀，加热至90℃～120℃反应3小时，获得反应物混合物143.25Kg，其中脱硫脱硝剂为88.75Kg，水54.5Kg。然后再向该143.25Kg脱硫脱硝剂水溶液中加入442.5Kg乙二醇和4.25Kg 蒸馏水，搅拌、混和，得脱硫脱硝剂含量为15％(w/w)、乙二醇含量为75％(w/w)、水含量为10％(w/w)的脱硫脱硝溶液590Kg。用该脱硫脱硝溶液进行如下试验：
用本脱硫脱硝溶液在图1所示的装置中按以上所述的实施方式运行，运行条件是：
T1＝30.6～36.5℃，T2＝21.6～28.2℃，T3＝125～127.1℃，T4＝123.8～127.1℃，T5＝103～118℃，T6＝27.8～29.9℃；
P1＝6.4～7kPa，P2＝2.6～2.85kPa，P3＝3.5～4.45kPa，P5＝0.95～1.55kPa；
F1＝164m3/hr，F2＝0.125m3/hr，F3＝19.7～20.2m3/hr，F4＝0～4.2m3/hr。
按照实施方法进行实验运行，取2015年1月7日晚班的运行数据如下：
处理前气体成分A1：SO2：1366.5～1977ppm，    NOX：未测，
                  CO2：3.3～8％(v/v)，      O2：23.7～24.9％(v/v)。
处理后气体成分A2：SO2：6～8.5ppm，          NOX：未测，
                  CO2：3.0～7.7％(v/v)，    O2：20.7～21.6％(v/v)。
         脱硫效率为：99.39％～99.58％。
再生释放气体成分A3：SO2：89.9％～90.1％(v/v)，   NOX：0.1％(v/v)，
                    CO2：1.5～2.9％(v/v)，       O2：未测。
富液成分A4：SO2：3.959～6.331g/L，               NOX：未测，
            pH：3.14～3.64。
贫液成分A5：SO2：0.446～0.522g/L，               NOX：未测，
            pH：4.16～4.19。
冷凝热水成分A6：SO2：0.0011～0.0017g/L。
溶液4：由聚乙二醇200、柠檬酸和N-甲基二乙醇胺(MDEA)(1∶1∶1摩尔比)混合合成的脱硫脱硝剂含量为15％(w/w)、聚乙二醇200含量75％(w/w)、水含量10％(w/w)组成的脱硫脱硝溶液。
本脱硫脱硝剂的合成方法是：先将柠檬酸48Kg溶解在50Kg蒸馏水中，然后再向柠檬酸水溶液中慢慢加入29.75Kg N-甲基二乙醇胺(MDEA)，同时慢慢冷却，使温度不超过50℃，溶解彻底以后，形成了柠檬酸MDEA溶液，再向柠檬酸MDEA溶液中加入50Kg聚乙二醇200，搅拌均匀，加热至90℃～120℃反应3小时，获得反应物混合物177.75Kg，其中脱硫脱硝剂为173.25Kg，水54.5Kg。然后再向该177.75Kg脱硫脱硝剂水溶液中加入812.25Kg聚乙 二醇200和55.5Kg蒸馏水，搅拌、混和，得脱硫脱硝剂含量为15％(w/w)、聚乙二醇200含量为75％(w/w)、水含量为10％(w/w)的脱硫脱硝溶液1100Kg。用该脱硫脱硝溶液进行如下试验：
用本脱硫脱硝溶液在图1所示的装置中按以上所述的实施方式运行，运行条件是：
T1＝28.6～31.8℃，T2＝25.7～27℃，T3＝120.5～121.7℃，T4＝112.9～113.7℃，T5＝105～105.5℃，T6＝67.3～73.4℃；
P1＝8.89～9kPa，P2＝1.95～2.15kPa，P3＝2.15～3.1kPa，P5＝1.75～2.35kPa；
F1＝140m3/hr，F2＝0.202m3/hr，F3＝19.7～20.2m3/hr，F4＝0～4.2m3/hr。
按照实施方法进行实验运行，取2015年2月11日晚班的运行数据如下：
处理前气体成分A1：SO2：1302～2815.5ppm，    NOX：49.8～459ppm，
                  CO2：4.7～5.6％(v/v)，    O2：20.6～20.7％(v/v)。
处理后气体成分A2：SO2：4～14.5ppm，         NOX：0～0.1ppm，
                  CO2：4.0～4.2％(v/v)，    O2：18.5～18.7％(v/v)。
         脱硫效率为：99.44％～99.65％；脱硝效率：100％。
再生释放气体成分A3：SO2：89.9％～90.1％(v/v)，     NOX：0～0.1％(v/v)，
                    CO2：4.1～9.6％(v/v)，         O2：未测。
富液成分A4：SO2：3.51～5.76g/L，             NOX：未测，
            pH：4.6～4.85。
贫液成分A5：SO2：0.19～0.22g/L，             NOX：未测，
            pH：5.34～5.58。
冷凝热水成分A6：SO2：0.004～0.423g/L。
由以上实验结果可以知道，本发明的脱硫脱硝剂效果较好，可以用于实际的工业化中脱除气体中的二氧化硫和氮氧化物。

Claims (10)

  1. 一种脱硫脱硝剂，是由多醇和/或聚多醇类物质、多元羧酸类物质和碱性物质混合，加热到90℃以上，经缩合和/或聚合后得到的大分子或高分子的醚类和/或酯类物质，其中所述多醇是指分子中含有二个或二个以上羟基基团的有机化合物；所述聚多醇类物质是一个多醇分子中的羟基与另一个多醇分子中的羟基缩合失去一个水分子而形成醚键，这样以醚键的方式连接的高分子或大分子物质；所述多元羧酸类物质是在同一分子中至少含有两个或两个以上羧基的化合物；所述碱性物质是无机碱性物质和/或有机碱性物质。
  2. 如权利要求1所述的脱硫脱硝剂，其特征在于，所述多醇选自下列化合物中的一种或多种：乙二醇、丙二醇、1，2，3-丙三醇、1，2-丁二醇、1，3-丁二醇、1，4-丁二醇、2，3-丁二醇、1，4-丁烯二醇、戊二醇、新异戊二醇、异戊二醇、1，5-戊二醇、1，6-己二醇、苯二酚、1，2，4-丁三醇、异丁三醇、戊三醇、异戊三醇、苯三酚、季戊四醇、戊四醇、异戊四醇、丁四醇、没食子酸和单宁。
  3. 如权利要求1所述的脱硫脱硝剂，其特征在于，所述聚多醇类物质选自下列物质中的一种或多种：聚乙二醇、聚丙二醇、聚丁二醇、聚丙醇、聚丁醇、聚乙二醇一甲醚、聚乙二醇二甲醚、聚乙二醇一乙醚、聚乙二醇二乙醚。
  4. 如权利要求1所述的脱硫脱硝剂，其特征在于，所述多元羧酸类物质选自下列化合物中的一种或多种：乙二酸、丙二酸、丁二酸、氨基乙二酸、氨三乙酸、EDTA、酒石酸、鞣质酸、多聚没食子酸和柠檬酸。
  5. 如权利要求1所述的脱硫脱硝剂，其特征在于，所述无机碱性物质包括氨以及碱金属、碱土金属或过渡金属的氢氧化物、碳酸盐、羧酸盐和络合物。
  6. 如权利要求1所述的脱硫脱硝剂，其特征在于，所述有机碱性物质为有机胺类物质，选自脂肪胺、芳香族胺和醇胺类，所述脂肪胺选自：甲胺、二甲胺、三甲胺、一乙胺、二乙胺、三乙胺、一丙胺、二丙胺、三丙胺、正丙胺、异丙胺、一丁胺、二丁胺、三丁胺、正丁胺、仲丁胺、异丁胺、叔丁胺、乙二胺、丙二胺、己二胺、三亚乙基二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、多亚乙基多胺、环戊胺、环己胺和环庚胺；所述芳香族胺选自：苯胺、N-甲基苯胺、N-乙基苯胺、N-丙基苯胺、N-丁等基苯胺、N,N-二甲基苯胺、N,N-二乙基苯胺、N,N-二丙基苯胺、N,N-二丁基苯胺、苯二胺、α-萘胺、卤代苯胺、硝基苯胺和磺酸基苯胺；所述醇胺类选自：一甲醇胺、二甲醇胺、三甲醇胺、一乙醇胺、二乙醇胺、三乙醇胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N,N-二异丙基乙醇胺、N- 甲基二乙醇胺、一丙醇胺、二丙醇胺、三丙醇胺、异丙醇胺、二异丙醇胺、三异丙醇胺、一丁醇胺、二丁醇胺、三丁醇胺、N-羟乙基乙二胺、N,N’-二羟乙基乙二胺、N,N-二羟乙基苯胺、N-乙基-N-羟乙基苯胺、N-甲基-N-羟乙基苯胺、邻氨基苯酚、间氨基苯酚、对氨基苯酚、2,4,6-三(二甲氨基甲基)酚、3-二乙胺基苯酚、2-氨基-5硝基苯酚、氨噻肟酸、N-甲基吡咯烷醇、2,4-二氨基-6-羟基嘧啶、三聚氰酸、2-(2’-羟基-5’-甲基苯基)苯并三唑、γ酸、J酸、苯基J酸、芝加哥酸及其盐、H酸及其盐、双J酸、猩红酸及其盐。
  7. 如权利要求1所述的脱硫脱硝剂，其特征在于，多醇和/或聚多醇类物质∶多元羧酸类物质∶碱性物质的摩尔比为：10∶0.5～2∶0.1～3，优选为1∶0.7～1∶0.3～2，更优选为1∶0.9～1.3∶0.5～1.5，极优选为1∶0.9～1.1∶0.5～1.2，最优选为1∶1∶0.5～1。
  8. 一种脱硫脱硝溶液，是在乙二醇和/或聚乙二醇和/或水组成的溶液中加入权利要求1～7任一所述的脱硫脱硝剂形成的溶液，其中所述脱硫脱硝剂的含量为0.1-50wt％，优选2-30wt％，更优选5-25wt％，最优选10-20wt％。
  9. 权利要求1～7任一所述的脱硫脱硝剂在气体脱硫和/或脱硝工业中的用途，用于同时脱除气体中的二氧化硫和氮氧化物，或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。
  10. 如权利要求9所述的用途，其特征在于，所述气体是烟道气、焚烧气、焦炉气、染料厂合成废气、化纤厂排污气，或含SOx和/或NOX的其它工业原料气或废气。
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