CN114797418B - Novel process for deep dedusting, desulfurization and denitrification of flue gas and efficient energy-saving equipment system - Google Patents
Novel process for deep dedusting, desulfurization and denitrification of flue gas and efficient energy-saving equipment system Download PDFInfo
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- CN114797418B CN114797418B CN202110072141.4A CN202110072141A CN114797418B CN 114797418 B CN114797418 B CN 114797418B CN 202110072141 A CN202110072141 A CN 202110072141A CN 114797418 B CN114797418 B CN 114797418B
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- flue gas
- amino acid
- desulfurization
- glycine
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- 239000003546 flue gas Substances 0.000 title claims abstract description 110
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 72
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 63
- 230000023556 desulfurization Effects 0.000 title claims abstract description 63
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000000428 dust Substances 0.000 claims abstract description 74
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000746 purification Methods 0.000 claims abstract description 49
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- 150000003839 salts Chemical class 0.000 claims abstract description 30
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- 238000005507 spraying Methods 0.000 claims abstract description 18
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- 238000010521 absorption reaction Methods 0.000 claims description 87
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- OFNJDDJDXNMTHZ-UHFFFAOYSA-L calcium;2-aminoacetate Chemical compound [Ca+2].NCC([O-])=O.NCC([O-])=O OFNJDDJDXNMTHZ-UHFFFAOYSA-L 0.000 claims description 27
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- 239000004473 Threonine Substances 0.000 description 1
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- 239000003929 acidic solution Substances 0.000 description 1
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- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 description 1
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- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
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- FDIWRLNJDKKDHB-UHFFFAOYSA-N azanium;2-aminoacetate Chemical compound [NH4+].NCC([O-])=O FDIWRLNJDKKDHB-UHFFFAOYSA-N 0.000 description 1
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- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 235000018417 cysteine Nutrition 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
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- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- 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
- B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
- B01D47/06—Spray cleaning
-
- 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to a novel process for integrating dust removal, desulfurization and denitrification by using amino acid and/or amino acid soluble salt as a treatment working solution of a deep desulfurization and denitrification purification system and a high-efficiency energy-saving equipment system applying the novel process, which are characterized in that high-temperature flue gas is subjected to ammonia-free denitration by catalytic spraying, desulfurization, denitrification and decarburization by using a mixture of amino acid and amino acid soluble salt, and purified flue gas is sprayed and washed by supplementing clean water through a purification tower filled with a wire mesh filler, so that deep purification or ultralow emission of the flue gas can be realized. By using the amino acid and/or the amino acid soluble salt as the desulfurization circulating working solution, the desulfurization rate of nearly 100% can be achieved between pH6 and 7, meanwhile, the escaped ammonia is absorbed, the influence of the escaped ammonia on dust is eliminated, and the ammonia can be recycled in the reproduction stage. The process has the advantages of simple flow, low investment, low purification cost and good purification effect, and can realize the recycling of wastes.
Description
Technical Field
The invention relates to a novel process for deeply purifying flue gas by dust removal, desulfurization and denitration and a high-efficiency energy-saving device system, belonging to the field of energy conservation and environmental protection.
Background
Traffic, industry and agriculture are the main sources of atmospheric pollutants such as dust, sulfur dioxide, nitrogen oxides, volatile organic compounds and the like. Boiler flue gas is an important point of treatment as a "point" pollution source.
At present, the flue gas dust removal, desulfurization and denitrification all adopt independent and separate treatment schemes. The simplest denitration scheme with low investment is a denitration method (NSCR) which directly sprays ammonia or ammonium salt into high-temperature flue gas to directly and non-catalytically reduce nitrogen oxides, but has limited effect, and the reduction reaction of ammonia or ammonia water or ammonium bicarbonate or urea solution and nitrogen oxides (NOx) can be carried out when the flue gas temperature in a coal-fired boiler is 800-1200 ℃, and the denitration efficiency is reduced but is only 30-70%. The catalytic reduction method has large investment (SCR), the denitration efficiency can reach about 75%, but the ultra-low emission requirement is difficult to reach, because the denitration efficiency can be improved by using excessive ammonia, but ammonia escape and dust exceeding are caused; the flue gas and sodium bicarbonate dry powder are reacted in a circulating fluidized bed reactor for denitration, then sodium bicarbonate solution is used for spray desulfurization in a desulfurizing tower, ozone or nitrogen dioxide is introduced for oxidation, absorption, regeneration and drying are carried out to obtain sodium bicarbonate, and the improved process for recycling is adopted, but the problems of complex process, high investment and operation cost, unsatisfactory effect and the like still exist. The mature technology of ultralow emission is a low-nitrogen combustion SCR3+1 catalytic layer, the denitration efficiency can be more than 85%, but the catalyst is easy to deactivate. The investment intensity of the denitration of the general industrial boiler reaches the general emission standard of 80 yuan/KW, and the denitration reaches the ultra-low emission standard of 120 yuan/KW.
The dry desulfurization of the limestone powder and the limestone-gypsum wet desulfurization of the limestone powder are not high in efficiency, and in order to reach the new standard of flue gas emission or the ultra-low emission standard with higher requirements, wet desulfurization processes such as a sodium method, an ammonia method or a double-alkali method are required to be used, and a combination method of connecting double towers in series or adding tower height, spraying layers, circulating spraying quantity and the like is adopted. The sodium method has the highest cost, the alkali concentration of the lime method and the double-alkali method is limited by dissolution balance, the alkali concentration cannot be increased, ammonia salt formed can not play a role when the pH value is smaller than 7 in ammonia desulfurization, ammonia escapes seriously when the pH value is larger than 7, and the problems of secondary pollution, low ammonia utilization rate, excessive dust and the like exist, so that even if the circulating amount is increased on the basis of the gas-liquid ratio being larger than 1000:20, the standard emission is difficult. The method has the advantages of large investment, high operation cost, high energy consumption and limited space, and is difficult to reach new emission standards and ultralow emission requirements, so that the method is a common problem faced by the current flue gas purification, and high-sulfur coal cannot be used, so that resource waste and cost rise are caused. The wet desulfurization purification flue gas has low temperature, high humidity and entrained aerosol, so that dust cannot reach the standard, cloth bag dust removal cannot be used, wet electric dust removal or electric bag dust removal efficiency can be more than 99.9%, but the inlet dust concentration is limited as well. The investment intensity of the common industrial boiler for desulfurizing reaches the common emission standard is 100 yuan/KW, and the investment intensity reaches the ultralow emission standard is 150 yuan/KW.
Mechanical dust removal, cloth bag dust removal, electric dust removal, washing dust removal, wet electric dust removal and the like are currently several common dust removal modes. The mechanical dust removal relies on gravity and centrifugal force to remove part of dust, has a simple structure, and is low in equipment cost and operation cost, but the dust removal efficiency is low. The electrostatic dust collection utilizes electrostatic attraction force to remove dust, the airflow resistance is small, the dust collection efficiency is more than 99%, but the investment is high, and the equipment size is large. The bag-type dust collector ensures that dust-containing air flows are combined with the filter bags to collect dust particles, and the dust collection efficiency can reach 99 percent, but is not applicable to dust collection of high temperature and moisture. The investment intensity of the general industrial boiler for dust removal reaching the general emission standard is 30 yuan/KW, and the investment intensity of the general industrial boiler for dust removal reaching the ultra-low emission standard is 100 yuan/KW.
At present, the flue gas desulfurization, denitrification, dust removal and purification are all combined by the technology. The dust particles, sulfur dioxide and other pollutants are required to be contacted with liquid drops or liquid films in a gas phase or on the surface of a filler to react to capture dust through dilute alkali water spraying, the dust removal and desulfurization efficiency can reach more than 95%, but the problems that the purification effect is poor, the treatment cost is high, and the national ultra-low emission standard (the allowable emission concentration of sulfur dioxide, dust and nitrogen oxides is not higher than 35mg/Nm 3、10mg/Nm3、100mg/Nm3 respectively under the condition of 8% of standard oxygen content) cannot be met still exist.
The existing flue gas purification technology has the defects of complex process route and large equipment investment, and can generally remove more than 95 percent of sulfur oxides, more than 80 percent of nitrogen oxides and more than 99 percent of dust. The investment intensity of the general industrial boiler comprehensively reaching the general emission standard is 210 yuan/KW, and the ultra-low emission standard is 370 yuan/KW.
Therefore, the development of a novel process and high-efficiency energy-saving equipment for realizing the ultralow emission of the flue gas integrating desulfurization, denitrification and dedusting has great significance, along with simplicity, high efficiency, low investment and low running cost.
Disclosure of Invention
The problems of large gas quantity, low sulfur dioxide concentration, low alkali concentration of conventional desulfurizing liquid, poor atomization effect, low denitration efficiency, ammonia escape, dust overstandard and the like of industrial flue gas lead to unsatisfactory dedusting, desulfurizing and denitrating effects. The technology of simulating tornadoes is utilized in the ammonia process and the double-alkali process to realize full atomization of the purifying liquid and full mixing and contact with the cyclone flow of the flue, so that the circulating spray liquefaction amount is reduced by more than 90%, ammonia escape is effectively prevented, remarkable energy saving and consumption reduction and deep purification of flue gas are realized, the problems that the emission of nitrogen oxides reaches the standard, the alkali concentration of the solution is improved and the quality of desulfurized gypsum is improved still can not be solved, and the potential for reducing the liquid-gas ratio and the circulating amount is not great. Dust entrainment and typical pollutants of the cyclone atomization tail gas still cannot reach ultra-low emission at the same time. Aiming at the problems and the defects, the invention innovates a novel process for deeply purifying flue gas and an efficient energy-saving equipment unit which are integrated with desulfurization, denitrification and dedusting and take amino acid (including mixed amino acid) and/or salt thereof as a purifying working solution.
The flue gas desulfurization by the ammonia method is a currently preferred deep desulfurization process, because the consumption material is ammonia in water, the solid production amount is small, the blockage is not easy to happen, but the secondary environmental pollution caused by ammonia escape and the problems of ammonium sulfate outlet and seasonal sales exist. Thus, there is a wait improvement. The research shows that amino acid and its salt are easy to dissolve in water, non-volatile, easy to raise concentration, free of ammonia escape, and the mixed water solution of amino acid and its soluble salt with pH greater than 3 (hereinafter, the mixed water solution of amino acid and its soluble salt is referred to as desulfurizing liquid for short) has excellent desulfurizing effect, and sulfur dioxide is not distilled out under the temperature condition of below 100 deg.c, and the desulfurizing liquid may be regenerated circularly with calcium amino acid-containing solution, and has nano calcium sulfate as by-product meeting the quality requirement. Further studies have found that amino acids are not effective in absorbing carbon dioxide, but that monovalent salts of amino acids neutralize two protons, and that monovalent aqueous solutions of amino acids having a pH greater than 8 (decarbonizing solutions) are effective in absorbing carbon dioxide to produce amino acid-sodium bicarbonate solutions. Industrial implementation further proves that the aqueous solution containing amino acid monovalent salt sprayed into the hot flue gas and fully atomized can quickly react with sulfur dioxide and carbon dioxide in the flue gas to generate sodium sulfite and sodium bicarbonate with reducibility, the generated sodium bicarbonate and amino acid carbonate have the same desulfurization effect, and the sodium sulfite has the deep denitration effect of reducing nitrogen oxides. Sodium sulfate or sodium sulfite can be removed by adding lime, carbide slag and amino acid calcium in a precipitation way, and the regenerated amino acid monovalent salt returns to the system for recycling, so that the generated calcium sulfate can be developed into a high-cost-performance modified nano calcium-based new material. Therefore, the amino acid and/or amino acid monovalent salt-amino acid system is not only an ideal desulfurization, denitrification and ammonia capturing and purifying system, but also an ideal system for high-efficiency decarburization and combination of nano calcium sulfate or nano calcium carbonate.
The invention relates to a novel dust removal, desulfurization and denitration integrated process and a high-efficiency energy-saving equipment system which take amino acid and/or amino acid monovalent salt-amino acid as a deep desulfurization, denitration and ammonia capturing purification system.
In particular, the invention provides a novel process for flue gas catalytic-free ammonia injection primary denitration, deep dedusting, desulfurization and denitration of amino acid or amino acid salt circulating liquid and ammonia capture, which is characterized in that: directly spraying ammonia into high-temperature flue gas to perform catalytic-free denitration, using an aqueous solution containing amino acid and/or amino acid soluble salt as a flue gas treatment working solution to perform deep purification to obtain an absorption liquid, recycling and recycling the absorption liquid, and spraying and washing the deeply purified flue gas to realize the re-purification of the flue gas so as to meet the ultra-low emission requirement.
Preferably, in the above process, the amino acid is an organic acid having an amino group substituted, and the position of the amino group in the organic acid is not limited to the α -position, and may be any of the β -position, γ -position, and the like of the organic acid. Preferably, the amino group in the amino acid is located at the alpha position of the organic acid. Particularly preferred amino acids are glycine, alanine, 4-aminobutyric acid, 3-aminopentanoic acid, 5-aminopentanoic acid, valine, leucine, isoleucine, methionine (methionine), proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine or pyrrolysine, or amino acids are proteolytic mixed amino acids. Preferably, the amino acid is one or more of glycine, glutamic acid or a proteolytic mixed amino acid.
Preferably, in the above process, the amino acid soluble salt is a monovalent salt, divalent salt or trivalent salt of an amino acid having a solubility in water of more than 10g/100ml, or a mixture of a plurality of monovalent, divalent or trivalent salts of an amino acid having a solubility in water of more than 10g/100ml, and particularly preferably, the amino acid soluble salt is a sodium, potassium, ammonium, calcium salt or the like of an amino acid.
Preferably, in the above process, the absorption liquid is used for recycling, so that the amino acid in the absorption liquid can be recycled. Preferably, the recycling method is to react the absorption liquid with calcium hydroxide or soluble amino acid calcium to remove one or more of sulfate radical, sulfite radical or carbonate radical. One or more of insoluble calcium sulfate, calcium sulfite or calcium carbonate is produced, and the produced amino acid can be recycled.
Preferably, the flue gas treatment working fluid is a mixed aqueous solution of one or more of glycine, glycine sodium salt, glycine calcium salt, glycine potassium salt and glycine ammonium salt.
Preferably, the mass content of one or more of glycine, glycine sodium salt, glycine calcium salt, glycine potassium salt and glycine calcium salt (glycine and its soluble salt mixture) in the mixed aqueous solution is 1-30wt% based on the mass of glycine, preferably, in order to increase the amount of sulfur oxide and carbon dioxide in the flue gas and reduce the amount of circulating materials, the concentration of glycine and its soluble salt mixture in the mixed aqueous solution is preferably close to saturation.
Preferably, in the process, the spray washing is to continuously spray wash the filler layer and the flue gas by using the supplementing water at the top of the wire mesh filler tower so as to prevent the entrainment of aerosol, ensure the deep purification effect and meet the ultra-low emission requirement. The wire mesh packing tower is a washing tower, a carbonization tower, a dust removal tower or a demisting tower which adopts spherical wire mesh packing, the spherical wire mesh packing is a porous hollow body sphere, the pore size of the wire mesh is between 0.1mm and 6mm, and the wire mesh packing tower is provided with a wire mesh structure. Preferably, in the process, the ammonia spraying step improves the denitration efficiency by optimizing the dosage of ammonia water, the position of a spray head and the enhanced mixing effect, and simultaneously controls the pH value of the flue gas treatment working solution to be less than or equal to 7 in the deep purification step so as to ensure desulfurization and denitration and ammonia capture, thereby meeting the ultra-low emission requirement.
Preferably, in the above process, the flue gas treatment working fluid is controlled to have a ph=4 to 7 in the deep purification step to ensure the desulfurization effect, and particularly preferably, the flue gas treatment working fluid has a ph=5 to 7 in the desulfurization and denitrification ammonia capturing step.
Preferably, in the above process, the flue treatment working solution is sodium glycinate-glycine mixed aqueous solution or glycine-calcium glycinate mixed aqueous solution, the flue treatment working solution is used for realizing high-efficiency desulfurization, deep denitration and ammonia capture, and the absorption solution after desulfurization and denitration is treated by calcium hydroxide or calcium glycinate, so as to obtain the circulating mixed working solution containing one or more of sodium glycinate, calcium glycinate or glycine by regeneration, and ammonia and co-production of nano calcium sulfate and calcium carbonate are simultaneously recovered.
Preferably, the pH of the sodium glycinate-glycine mixed aqueous solution or the calcium glycinate mixed aqueous solution is between 6 and 7. The mixed aqueous solution with the pH value between 6 and 7 can reach approximately 100 percent of desulfurization rate and more than 30 percent of denitration rate, and simultaneously absorb escaped ammonia, so that the influence of the escaped ammonia on dust is eliminated, and the ammonia can be recycled in the reproduction stage. In the sodium glycinate-glycine mixed aqueous solution, the molar ratio of sodium glycinate to glycine is 1:0.1-10.0, and preferably, the molar ratio of sodium glycinate to glycine is 1:0.2-5.0.
The process has the advantages of simple flow, low investment, low purification cost and good purification effect, and can realize the recycling of wastes.
Preferably, in the above process, the flue treatment working solution is a calcium glycinate aqueous solution, the calcium glycinate aqueous solution is used for decarbonizing the flue gas to produce nano calcium carbonate, carbon dioxide in the flue gas is effectively removed and utilized, or the filtered absorption solution with the pH of about 8 is used for reacting with amino acid calcium, preferably calcium glycinate to produce nano calcium carbonate, and the decarbonizing circulating solution is regenerated.
In the above process, the pH is about 8 and ph=7 to 9, and particularly preferably, the pH is about 8 and ph=7.5 to 8.5.
Preferably, in the above process, the method for recycling the absorption liquid comprises the following steps: the filtered absorption liquid with the pH value of about 5 is reacted with the amino acid calcium to prepare the nano calcium sulfate with the purity meeting the requirement, and the amino acid calcium is preferably calcium glycinate.
Preferably, in the above process, the pH of the filtered absorption liquid is 4 to 6, preferably, the pH of the filtered absorption liquid is 4.5 to 6.5.
In order to inhibit dust exceeding caused by aerosol entrainment, a filling wire mesh filling tower is specially arranged, and the ultra-low emission of flue gas is ensured by supplementing clean water to continuously wash the purifying tower. The denitration efficiency can be effectively improved by optimizing the dosage of ammonia water, the position of a spray head and enhancing the mixing effect, the pH range of the flue gas treatment working solution of amino acid and soluble salt thereof is controlled within the range of 5-7, the desulfurization, denitration and ammonia capturing effects can be ensured, the targets of deep purification and ultralow emission are realized, and preferably, the amino acid and the soluble salt thereof are glycine and the soluble salt thereof.
Preferably, in the process, the dust removing tower is provided with one or more rotary spray heads at the bottom, the middle or every 3-5m of the dust removing tower to generate a simulated "tornado" effect, and a continuous spraying device for supplementing clear water is arranged at the top. The rotary spray head consists of a stator and a rotor, the rotor is provided with a fluid cavity, a power nozzle and a direct-injection nozzle, and the rotor can generate rapid rotation by means of the reaction force of the fluid sprayed from the power nozzle and the small resistance advantage of a bearing, the rotation speed in liquid or air can be varied from hundreds to tens of thousands times per minute, and the rapid rotation of the air flow and the liquid flow not only can drive the peripheral gas and the liquid to rotate, but also can greatly promote the contact friction of the dispersion fluid and a medium, and strengthen the dispersion or atomization effect.
Preferably, in the process, the mode of enhancing the mixing effect is to add an arc-shaped guide plate matched with the radian of the dust removal tower at the flue gas inlet to guide the flue gas to enter the dust removal tower tangentially.
Preferably, in the above process, the ph=7-9 of the flue treatment working solution is controlled, at this time, the tower functions to decarbonize and absorb carbon dioxide to prepare nano calcium carbonate, or the pH of the flue treatment working solution is 5-7, and the tower functions to desulphurize, so that the desulfurization effect can be ensured and ammonia is prevented from escaping.
Preferably, in the process, the mixed aqueous solution of sodium glycinate-glycine can be sprayed for high-efficiency desulfurization and further denitration to obtain absorption liquid, and then calcium hydroxide or amino acid calcium, preferably calcium glycinate, is added into the absorption liquid to co-produce nano calcium sulfate and calcium carbonate, and simultaneously glycine is regenerated and ammonia is recovered.
Preferably, in the process, calcium glycinate is used for desulfurization and dust removal, nano calcium carbonate is produced, carbon dioxide in flue gas is utilized, filtered absorption liquid with pH of 7-9 is reacted with amino acid calcium, preferably calcium glycinate, and nano calcium carbonate is co-produced, so that the absorption liquid is recycled.
Preferably, in the above process, the filtered absorption liquid with pH of 4-6 is reacted with amino acid calcium, preferably calcium glycinate, to synthesize nano calcium sulfate with the purity meeting the requirement, preferably, the calcium glycinate is recycled byproduct calcium glycinate, so that the absorption liquid is recycled.
The invention also provides application of the process, the process is used for dedusting, desulfurizing and denitrating any flue gas conventionally required or is updated and transformed into ultra-low emission purifying equipment, the operation cost is reduced through energy saving, consumption reduction and byproduct utilization, and the economic benefit is improved.
Preferably, in the application, the equipment is equipment which is used for carrying out high-efficiency deep dust removal, desulfurization and denitrification through gas-liquid film mass transfer with a wire mesh spherical packed tower, and can be widely used for purifying and recycling various flue gases, so as to meet the requirements of low-cost investment, low-cost operation and ultra-low emission.
The tracking result of the experimental demonstration device proves that under neutral and weak acid conditions, the amino acid or amino acid monovalent salt mixed system is efficiently desulfurized and significantly denitrated. The control experiment shows that the nano calcium carbonate can be synthesized and simultaneously desulfurized by directly introducing the flue gas by utilizing the amino acid calcium generated by dissolving calcium hydroxide or carbide slag. Preferably, the glycine or sodium glycinate-glycine mixed system is efficiently desulfurized and significantly denitrified under neutral and weakly acidic conditions. Calcium glycinate generated by dissolving calcium hydroxide or carbide slag with glycine is directly introduced into flue gas to synthesize nano calcium carbonate and simultaneously desulfurize.
It should be noted that, due to electrostatic repulsion, mist droplets and dust in flue gas often form aerosol which is difficult to capture, and condensation is easy to affect cloth bag filtration, so that the electrostatic dust removal effect is not ideal. The water mist and water film washing method has the advantages of static electricity elimination, dust removal and desulfurization. The flue gas tail gas water purification technology has development potential.
In the patent CN104096434a, we have designed a principle of forming tornado, which makes the hot flue gas entering desulfurization rotate along the horizontal tangential direction and spiral rise, and meanwhile, the counter force generated when the circulating washing water with kinetic energy applied by the pump is sprayed out from the nozzle pushes the movable nozzle to rotate along the airflow direction, the rotating atomizing nozzle can effectively convert the potential energy obtained by water into kinetic energy for pushing the nozzle and gas to rotate and surface energy for promoting the liquid drops to be further dispersed, thus greatly increasing the opportunity and time of gas-liquid contact, strengthening the flue gas desulfurization and dust removal reaction and mass transfer process, small-flow rotating water mist, realizing rapid vaporization and cooling, enabling the volume of high-temperature flue gas to suddenly drop to form negative pressure, generating a spiral rising motion in the purifying tower under the guidance of a reasonably arranged spiral flow guide plate, changing the spiral rising motion of the flue gas into a spiral rising motion from the whole upward motion direction, enabling dust, sulfur dioxide, nitrogen dioxide and the like to have more opportunities to contact with atomized materials suspended in a system under the pushing of self power and centrifugal force generated by the spiral flow, or capturing the environment, and eliminating the moisture and the dust and mist, and the moisture and the static dust can be obviously eliminated. The fast moving gas-liquid cyclone accelerates and promotes the enrichment of dust and liquid with high specific gravity towards the wall surface, and the dust removing effect can be obviously enhanced. In addition, the flue gas rich in water vapor can generate secondary water mist in the rotating and cooling processes, and can also assist dust collection and effective separation. The effect can be further ensured by adopting a multi-tower series washing and multi-position up-down rotary spray purification device. The purified flue gas passes through a water distribution film forming tower filled with a metal wire mesh filler, so that the flue gas can be sufficiently racemized to remove dust and mist, the deep purification is realized, and the low concentration of dust is controlled.
The specific technical scheme of the invention is as follows: newly-built or original desulfurization equipment is utilized, equipment transformation and circulating working solution replacement are carried out, and an integrated flue gas deep purification mode of desulfurization, denitrification and dust removal is adopted. An arc-shaped guide plate matched with the radian of a dedusting tower (a washing tower) is additionally arranged at the inlet of flue gas to guide the flue gas to enter the dedusting tower tangentially, one or more rotary spray heads can be arranged at the bottom, the middle and the upper part (or every 3-5 m) of each section of dedusting tower according to specific conditions and requirements, desulfurizing liquid (namely, mixed aqueous solution of amino acid and soluble salt thereof) is sprayed out through a spray nozzle, and the spray heads automatically rotate by means of recoil force generated when spraying water (under the condition that the pressure is 5 kg and the flow is 3m 3/h, the rotating speed can reach more than 3000 r/min). The installation of the guide plate reduces the cross section of the gas outlet by 20% -80%, negative pressure formed by rapid cooling after the flue gas inlet can increase the flow rate of the gas, and the practical situation proves that the reasonable arrangement of the cyclone guide plate can not cause unsmooth gas flow.
The technology is to atomize and induce 'wind eyes' by a rotary nozzle, and centripetal force generated by the volume shrinkage of hot flue gas and the energy supplemented by a multi-stage nozzle promote a mixed system of flue gas with purification liquid droplets to flow in a long distance, rapid rotation and orientation, as shown in fig. 2.
The integrated high-efficiency desulfurization, denitrification and dust removal can be realized by a direct reduction and denitrification method (NSCR), an amino acid calcium or amino acid monovalent salt purification system, in particular to a novel calcium glycinate or sodium glycinate-glycine purification system, a high-efficiency rotational flow and spherical screen filler liquid film deep dust removal purification technology and equipment combination, and the ultra-low emission requirement can be met. The technology of the invention accords with the basic principle of technological innovation from big way to simple, is a subversion technology of flue gas purification, can better realize low investment, low operation cost, ultra-low emission, and huge economic, social and environmental benefits of industrial flue gas devices or reformation.
The preparation method and reaction principle of the NO/NO 2 mixed gas and the purified NO gas for the laboratory are as follows:
The mixed gas of the red brown NO and the NO 2 can be prepared in a laboratory by utilizing the reaction of Cu powder and dilute HNO 3, and the reaction formula is as follows:
Cu+HNO3→NO+NO2+Cu(NO3)2+H2O
After the mixed gas passes through a NaOH gas washing bottle, colorless pure NO gas can be obtained, and the following reaction exists in alkaline water:
NO2+NO+2NaOH→2NaNO2+H2O
2NO2+2NaOH→NaNO2+NaNO3+H2O
The NO/NO 2 mixture is the feed gas of experiments 1-5, and the pure NO gas after the absorption of NO 2 by the lye gas washing bottle is the NO feed gas of experiments 1-3.
3NO2+H2O→2HNO3+NO
HNO3+NaOH→NaNO3+H2O pH＞7
Pka=7.2 (acid dissociation constant)
HSO 4 -＝SO4 2-+H+ pka=1.98 (acid dissociation constant)
Amino acids such as glycine can be reacted as calcium extractants with calcium hydroxide, carbide slag, lime in aqueous solution to give a clear calcium glycinate solution. The sodium glycinate solution can absorb 1mol of carbon dioxide in theory under normal temperature and normal pressure, and the absorption rate of the carbon dioxide of the 1mol/L sodium glycinate solution is 94.5% under the condition of controlling the pH7.5 as an end point. The reaction principle for preparing vaterite type calcium carbonate by glycine method-liquid reaction is as follows:
according to the reaction formula, the concentration of sodium glycinate is the same as that of calcium glycinate, and the reaction (3) occurs instantaneously, so long as the reaction (1) product and the reaction (3) product are mixed, vaterite type calcium carbonate can be produced, and the specific flow can be seen in fig. 1.
The relevant reactions and redox potentials for the absorption of SO 2、CO2、NO2 and NO in the glycine-sodium glycinate system are as follows:
SO2+H2NCH2COONa→Na2SO3+H2NCH2COOH pH＞5
SO2+H2NCH2COOH→(H3NCH2COOH)2SO3 pH＜2
CO2+H2NCH2COONa→Na2CO3+H2NCH2COOH pH＞10
CO2+H2NCH2COONa→NaHCO3+H2NCH2COOH pH≈8
CO2+H2NCH2COOH→H3NCH2COOH·HCO3 pH＞8
Na2SO3+NaNO2→Na2SO4+N2pH＜7
Na2SO3+NO2→Na2SO4+N2pH＜7
Na2SO3+NO→Na2SO4+N2pH＜7
NO 2 reacts with water to form HNO 3 and NO, but in the actual industrial process for preparing HNO 3, NO is oxidized to NO 2, and then cooled to 40 ℃ and then absorbed by water under pressurized conditions to prepare HNO 3. The redox potential of each substance in the solution is shown in Table 1 below.
TABLE 1 Standard redox potential of related substances
As can be seen from the above table, the oxidation potential of oxygen is highest, and in neutral or weakly acidic solutions, NO 2 and HNO 2 can be oxidized to form nitrite or nitrate; at the same time, sulfite can be oxidized into sulfate. Further comparing it can be seen that the oxidation potential of nitrogen oxides is higher than that of sulfides, so in the system, nitrogen oxides are oxidants, sulfites are reducing agents, and under neutral or weak acidic conditions, nitrogen oxides can be reduced into nitrogen, and the nitrogen oxides cannot be enriched in the system; sulfite is oxidized to sulfate and can be removed by calcium sulfate formation or crystallization concentration separation. This can be demonstrated from the examples. In summary, the aqueous solution containing one or more of glycine, sodium glycinate or calcium glycinate is successfully denitrated at the system purification temperature of about 40 ℃ with wet-type partial acidity of flue gas, ammonia escape is avoided, reducing agents such as ammonia or urea or powerful oxidizing agents such as ozone or nitrogen dioxide are not needed, the process is simple, the investment is saved, and the purification cost is low.
The invention provides a novel process for integrating dust removal, desulfurization and denitrification by using amino acid or mixed amino acid and/or amino acid soluble salt as a treatment working solution of a deep desulfurization and denitrification purification system and a high-efficiency energy-saving equipment system applying the novel process, which are characterized in that high-temperature flue gas is subjected to ammonia-spraying denitration without catalysis, desulfurization, denitrification and decarburization by using a mixture of amino acid and amino acid soluble salt, and purified flue gas is sprayed and washed by using supplementary clean water through a purification tower filled with a metal wire mesh filler, so that deep purification or ultralow emission of the flue gas can be realized. Specifically, glycine and/or glycine soluble salt are used as desulfurization circulating working solution, so that the desulfurization rate of nearly 100% can be achieved between pH6 and 7, meanwhile, escaped ammonia is absorbed, the influence of the escaped ammonia on dust is eliminated, and the ammonia in the absorption solution can be recycled in a reproduction stage. The process has the advantages of simple flow, low investment, low purification cost and good purification effect, and can realize the recycling of wastes.
Drawings
FIG. 1 is a schematic diagram of the absorption of carbon dioxide and by-product calcium carbonate by calcium glycinate and the recycling of glycine.
Fig. 2 is a schematic illustration of a typical high efficiency purification device.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1: evaluation of Sulfur dioxide absorption Effect of sodium Glycine
SO2+NH2CH2COONa+H2O→NH3 +CH2COONa+HSO3 -
HSO3 -→H++SO3 2-
Sulfur dioxide is prepared by anhydrous sodium sulfite and sulfuric acid. Saturated glycine solution is prepared, equivalent NaOH is prepared into sodium glycinate solution, SO 2 is introduced at 70 ℃,60 ℃ and 50 ℃, the change of the pH value of the absorption liquid along with the introduced SO 2 is observed, and meanwhile, 30% NaOH solution is added after an absorption bottle to serve as secondary absorption, SO that whether SO 2 escapes or not is judged.
Glycine-Na 2SO3 -HCl solution was prepared to simulate equimolar sodium glycinate absorption of equimolar SO 2. The pH value of the solution is measured according to the proportion of glycine to Na 2SO3 to HCI=1:1:2 (molar ratio) and the proportion of glycine to Na 2SO3 to HCI=1:1:3 (molar ratio); the solution of glycine to Na 2SO3 to hci=1:1:3 (molar ratio) was added to NaOH to adjust the pH to 3, titrated with standard hydrochloric acid solution to ph=2.78 and ph=2.5. See table 2 for relevant results.
TABLE 2 experimental conditions and analytical results
Experiments show that the sulfur dioxide can be normally absorbed by introducing SO 2 under the condition of 70/60/50 ℃, when the pH of the absorption liquid is reduced to 3, no bubbles are observed in the secondary alkali liquid, which indicates that the absorption is complete, and sulfur dioxide cannot escape before the pH=3. The mixture is placed at room temperature overnight, and the content is unchanged. When the pH of the absorption liquid was below 3, bubbles were observed in the secondary absorption bottle, indicating a significant escape of sulfur dioxide. Neither the absorption bottle mass nor the sulfur dioxide concentration increased significantly, indicating that ph=2.5 is the saturated absorption concentration of sulfur dioxide, at which time the absorbed sulfur dioxide mass is significantly higher than the equimolar glycine mass. At ph=4, substantially equimolar absorption can be achieved. Glycine: na 2SO3: HCl=1:1:2 (molar ratio) was prepared to simulate an equivalent sulfur dioxide absorption system pH=1.8, and the acidity was higher than that of the absorption solution, probably due to the stronger acidity of hydrochloric acid.
In summary, sodium glycinate can absorb sulfur dioxide with equal molar quantity, cannot escape under the condition of the conventional wet desulfurization with the pH value being more than 3, and is suitable for reducing equipment corrosion, preventing sulfur dioxide gas from escaping and controlling the pH value of absorption liquid in flue gas purification to be about 5.
Example 2: evaluation of Sulfur dioxide absorption Effect of glutamate
Sulfur dioxide is prepared by anhydrous sodium sulfite and sulfuric acid. Sodium glutamate solution is prepared, and the sodium glutamate solution is prepared according to the proportion of glutamic acid to NaOH=1 to 1 (molar ratio) and 1 to 2 (molar ratio) to be used as flue gas treatment working solution, also called desulfurization solution, SO 2 is introduced at the temperature close to 50 ℃ of the flue gas desulfurization solution, the change of the pH value of the absorption solution along with the amount of introduced SO 2 is observed, meanwhile, 30% NaOH solution is added after an absorption bottle to serve as secondary absorption, SO as to judge whether SO 2 escapes, and specific results are shown in the following table 3.
TABLE 3 experimental conditions and analytical results
When SO 2 is introduced at 50 ℃ to enable normal absorption, no bubbles are observed in the secondary alkali liquor when the pH of the sodium glutamate absorption liquid is reduced to be before 4, which indicates complete absorption, and no bubbles are observed in the secondary alkali liquor when the pH of disodium glutamate is reduced to be before 3, which indicates complete absorption; the temperature of the absorption liquid is increased to be 70 ℃ for heat preservation, no bubbles appear in the secondary alkali liquid, which indicates that the absorbed sulfur dioxide can not escape under the condition, and the glutamic acid/glutamate is proved to be an alternative sulfur dioxide absorbent.
Example 3: evaluation of Sulfur dioxide absorption Effect of Mixed amino acid salt obtained by protein hydrolysis
The method is characterized in that a solution mainly containing various mixed amino acid sodium salt (amino acid/small peptide water-soluble liquid with solid content of 15%) obtained by alkaline hydrolysis of shrimp shell proteins is used as a flue gas treatment working solution (namely desulfurization solution), SO 2 is introduced under the condition of 50 ℃ (the temperature of the flue gas desulfurization solution), the change of the pH of the absorption solution along with the introduced SO 2 is observed, and meanwhile, a 30% NaOH solution is added after an absorption bottle to serve as secondary absorption, SO that whether SO 2 escapes or not can be judged, and specific results are shown in the following table 4.
TABLE 4 experimental conditions and analytical results
Experiments show that under the condition of 50 ℃, SO 2 is introduced to enable normal absorption, when the pH value of the mixed sodium amino acid solution as an absorption solution is reduced to 3, no bubbles appear in the secondary alkali solution, which indicates complete absorption, the temperature of the absorption solution is increased to 60/70 ℃ for heat preservation, no bubbles appear in the secondary alkali solution, and sulfur dioxide is amino acid/small peptide and salt thereof, which can also be used as a desulfurization working solution.
Example 4: absorption conversion of nitrogen oxides (NOx) in aqueous solutions
1. NO/NO 2 pure water absorption blank control experiment
(1) Adding a certain amount of water, heating at 60-70deg.C, introducing NO/NO 2 for half an hour, and measuring the content of NO 3 - in the absorption liquid (number 1);
(2) Adding a certain amount of water, heating at normal temperature, introducing NO/NO 2 for half an hour, and measuring the content of NO 3 - in the absorption liquid (number 2);
2. NO/NO 2 absorption experiment
(1) Preparing 15% glycine solution, neutralizing with sodium hydroxide equivalent, heating at 60-70deg.C, introducing NO/NO 2 for half an hour, and measuring the NO 3 - content (number 3) in the absorption liquid;
(2) Preparing a glycine solution with concentration of about 15%, adding a certain amount of sodium hydroxide, adjusting pH to be 5-6, heating at 60-70 ℃, introducing NO/NO 2 for half an hour, and measuring the content of NO 3 - in the absorption liquid (number 4);
(3) Preparing a glycine solution with the concentration of 15%, neutralizing with sodium hydroxide with equivalent weight, heating at 60-70 ℃, introducing SO 2 and CO 2 to the pH value of 4-4.5, stopping introducing SO 2 and CO 2, introducing NO/NO 2 for half an hour, and measuring the content of NO 3 - in the absorption liquid (number 5);
3. NO absorption experiment
(1) Preparing a glycine solution with the concentration of about 15%, neutralizing with sodium hydroxide equivalent, heating at 60-70 ℃, introducing NO for half an hour, and measuring the content of NO 3 - in the absorption liquid (number 6);
(2) Preparing a glycine solution with concentration of about 15%, adding a certain amount of sodium hydroxide, adjusting pH to be 5-6, heating at 60-70 ℃, introducing NO for half an hour, and measuring the content of NO 3 - in the absorption liquid (number 7);
(3) About 15% glycine solution was prepared, neutralized with an equivalent of sodium hydroxide, and SO 2 and CO 2 were introduced at 60-70℃to pH=4-4.5, and the introduction of SO 2 and CO 2 was stopped, and then NO was introduced for half an hour, to thereby measure the NO 3 - content in the absorbent (No. 8). See table 5 for relevant results.
Table 5 shows the results of the experiment and analysis (absorption temperatures are 60 ℃ C.)
As can be seen from table 5, the NO/NO 2 mixture has poor solubility in water at higher temperatures in pure water systems (see experiment No. 1); introducing NO/NO 2 mixed gas at a lower temperature, wherein the concentration of NO 3 - is obviously increased (see experiment No. 2); the NO/NO 2 mixed gas has obvious concentration increase of NO 3 - in alkaline sodium glycinate solution, and proves that a sodium glycinate system can obviously absorb nitrogen oxides (see experiment No. 3), and has lower concentration of NO 3 - in acidic sodium glycinate solution (see experiment No. 4-5), and the nitrogen oxides can be obviously reduced according to the on-site desulfurization detection result, so that the reaction that sodium sulfite directly reduces the nitrogen oxides in gas and nitrite in solution is proved.
Example 5: oxidation-reduction reaction verification between nitrate, nitrite and sulfite
1. Oxidation-reduction verification of sodium nitrite, sodium sulfite and glycine
Mixing sodium nitrite, sodium sulfite and glycine according to the proportion of 1:1:1, and respectively reacting for 3 hours at the pH value of 4-8, the temperature of 30 ℃ and the temperature of 80 ℃. After the reaction, the content of the reducing substances (calculated by sodium nitrite) and the content of nitrate under different conditions are respectively measured, and the experimental conditions and specific analysis data are shown in Table 6.
TABLE 6 analysis of redox reaction results of sulfite-nitrite-glycine systems
2. Nitrate and sulfite redox validation
Mixing potassium nitrate and sodium sulfite according to the proportion of 1:1, and respectively reacting for 3 hours at the pH value of 5-10, the temperature of 30 ℃ and the temperature of 60 ℃. After the reaction, the content of the reducing substances (calculated by sodium nitrite) and the content of nitrate under different conditions are respectively measured, and the experimental conditions and specific analysis data are shown in Table 7.
TABLE 7 redox data sheet for sulfite-nitrate systems
It can be seen that nitrite and nitrate can be reduced by sulfite, and are more easily converted under neutral or weak acidic conditions, and nitrate or nitrite enrichment can not be generated in the solution under the treatment condition of about 40 ℃ under the pH range of 5-6.
Example 6: flue gas purification process tracking of carbon dioxide absorption by sodium glycinate
And (3) measuring the end point of absorbing carbon dioxide by sodium glycinate and measuring the temperature of removing carbon dioxide from the absorbing liquid. To the prepared 14% aqueous sodium glycinate solution, carbon dioxide was added at 30℃and 60℃to an end point pH at which the temperature was not changed any more and the measured carbon dioxide absorption amount were as shown in Table 6:
TABLE 8 absorption Effect and absorption Capacity in aqueous sodium glycinate solutions at different temperatures
Table 8 above shows that lower temperatures favor absorption of carbon dioxide with actual absorption rates of 70% and 63% of equimolar theoretical absorption rates, respectively. Additional experiments showed that glycine does not form salts and is very difficult to absorb carbon dioxide. The experimental results of the regeneration performance of the absorption liquid show that the suitable regeneration temperature is 110-115 ℃. The more economical and feasible co-production scheme is that the sodium glycinate solution absorbing carbon dioxide reacts with calcium glycinate to further synthesize vaterite type nano calcium carbonate, and the regenerated glycine and sodium glycinate mother solution are recycled.
Example 7: oxidative treatment and regeneration process analysis of sodium glycinate sulfur dioxide absorption liquid
Directly absorbing sulfur dioxide by using the prepared 15% sodium glycinate solution until the pH value reaches 3-4 to form sulfite, and then introducing air into the reactor, wherein the reaction is slower without stirring, but SO 3 2- is finally converted into SO 4 2- after 35 hours.
Saturated glycine solution was prepared, neutralized with equivalent NaOH, heated at 60℃and simultaneously passed through SO 2 and CO 2 to a pH of 3-4. The sodium glycinate solution absorbed with sulfur dioxide is treated with carbide slag, SO 3 2- is separated off first as CaSO 3, and CaSO 3 is then oxidized to CaSO 4. And continuously applying the filtrate after the carbide slag treatment to absorb flue gas. Stirring for one hour, precipitating for two hours, filtering to obtain solid and filtrate, and measuring the content of SO 3 2- and the content of residual Ca 2+ and glycine in the filtrate; stirring the solid with a proper amount of water, adjusting the pH to be 4.0-4.5, carrying out water bath at 45-50 ℃, introducing air for oxidation, precipitating, filtering to obtain the solid and filtrate, and measuring the SO 3 2- content in the solid.
TABLE 9 regeneration separation of sulfur dioxide-removed absorption liquid and post-application process material analysis
| Detecting items | One-time absorption | Secondary cover | Three times of application | Four times of application |
| Mass of solution before absorption | 174.76 | 246.74 | 271.27 | 316.67 |
| Absorbent liquid mass/g | 200 | 259.73 | 275.27 | 324.95 |
| SO 3 2- content/% | 15.14 | 10.46 | 3.77 | 5.49 |
| SO 3 2- content/% | 0.14 | 0.20 | 0.15 | 0.24 |
| Ca 2+ content/% | 0.43 | 0.32 | 0.30 | 0.30 |
| Glycine content/% | 11.88 | 7.30 | 5.89 | 4.18 |
| SO 3 2- content/%in L 1 of filtrate and wash water | 0.0288 | 0.0698 | 0.0338 | 0.020 |
| Ca 2+ content/%in L 1 of filtrate and washing water | 0.31 | 0.31 | 0.26 | 0.26 |
| Glycine content/%in L 1 of liquid and wash water | 8.55 | 6.18 | 4.92 | 3.84 |
| Glycine content/% | --- | --- | --- | 1.91 |
| Mass/g of solid after filtration | 107.75 | 99.42 | 43.34 | 66.77 |
| Glycine content/% | Not detected | Not detected | Not detected | Not detected |
| Dried solid mass/g | --- | --- | 23.02 | 43.04 |
| Quality/g of filtrate | 136.20 | 198.56 | 243.09 | 282.01 |
| Quality/g of wash water | 138.06 | 92.95 | 92.56 | 70.58 |
As can be seen from Table 9, the glycine loss was small, and the filtrate and the washing liquid were completely usable.
Example 8: glycine flue gas purification process tracking
The carbonization tower uses aqueous solution with glycine concentration of about 62g/L to carry out desulfurization, and the dust removal tower uses clear water. And sequentially starting a denitration system spray, a carbonization tower system spray, a water tank spray, a dedusting and demisting system spray and cutting into the flue gas. After the desulfurization is started, sulfate radical or sulfite is removed from the absorption liquid by calcium glycinate, a solution containing sodium glycinate and glycine is obtained and recycled to be used as a flue gas treatment working liquid, desulfurization and dust removal data are detected at a system outlet by using mobile detection equipment, the flue gas data are continuously monitored for 1 hour, the flue gas data are recorded once every 5 minutes, meanwhile, pH value values are recorded every 5 minutes, and the pH value results are shown in the following table 10.
TABLE 10 pH change of desulfurization and decarbonization solution
And detecting the data of the smoke and the dust of the inlet smoke after the outlet detection is finished. The results of the outlet and inlet measurements are shown in Table 11 below.
Table 11 inlet and outlet flue gas and smoke data
| Detecting items | Inlet port | An outlet |
| Standard dry flow m 3/h | 23996 | 18228 |
| Flue gas temperature DEG C | 128 | 39 |
| Moisture content% | 9.0 | 5.8 |
| Oxygen content% | 10.2 | 8.8 |
| Smoke concentration mg/m 3 | 19.7 | 3.19 |
| SO 2 concentration mg/m 3 | 262 | 3 |
| NOx concentration mg/m 3 | 137 | 75.1 |
And after the detection work is finished, switching the flue gas back to the chimney, and stopping spraying of the denitration system, spraying of the carbonization tower system, spraying of the water tank, and spraying of the dedusting and demisting system in sequence.
Example 9: evaluation of carbon dioxide absorption and removal effects of glycine and sodium glycinate
And sodium glycinate solution is used for circulating spraying, the desulfurization and dust removal effects are monitored, and meanwhile, the water loss of the system is monitored. The demisting tower uses low-concentration glycine mother liquor; the carbonization tower uses sodium glycinate solution with the concentration of about 51.2g/L and the pH value of 10.31.
And sequentially starting a denitration system spray, a carbonization tower system spray, a water tank spray, a dedusting and demisting system spray and cutting into the flue gas. After the flue gas is cut in, the sodium glycinate solution is firstly used as a flue gas treatment working solution, and the absorption solution generates corresponding calcium salt precipitation through calcium glycinate to generate calcium sulfate, sulfite and carbonate, so that the sodium glycinate-glycine solution is obtained and used as the flue gas treatment working solution for recycling. The results of the composition monitoring of the carbonization tower and the defogging tower are shown in tables 12 and 13 below.
TABLE 12 analysis of purifying liquid composition in carbonizing tower
TABLE 13 demister column purification liquid composition analysis
Example 10: flue gas purification effect of coal-fired boiler in glycine method system
The conditions associated with the purification of the flue gas of the coal-fired boiler at 45t by the sodium glycinate-glycine method are as follows:
The tower diameter is 2m, the tower height is 20m, the liquid spraying amount is 50m 3/h, the flue gas treatment working solution adopts sodium glycinate-glycine mixed water solution, the sodium glycinate-glycine mixed water solution is water solution with the concentration of sodium glycinate of 6.5% and the concentration of glycine of 5%, the absorption solution after absorbing the flue gas is recycled, namely calcium glycinate is used for precipitating sulfate radical, sulfite radical and carbonic acid radical to obtain calcium-containing precipitate, then the mixed solution containing sodium glycinate and glycine is obtained and used as the flue gas treatment working solution for recycling, and the pH value of the circulating solution is about 8. After the flue gas is absorbed by the flue gas treatment working fluid, the results of the inlet and outlet flue gas detection data are shown in tables 14 and 15 below.
Table 14 inlet and outlet flue gas detection data after 1 hour
| Detecting items | Inlet port | An outlet |
| Standard dry flow m 3/h | 31327 | 27386 |
| Flue gas temperature DEG C | 112 | 45 |
| Average flow rate m/s | 11.8 | 8.7 |
| Moisture content% | 9.0 | 3.9 |
| Oxygen content% | 8.1 | 8.4 |
| Smoke concentration mg/m 3 | 30.6 | 6.5 |
| SO 2 concentration mg/m 3 | 756 | 0 |
| NOx concentration mg/m 3 | 78 | 38 |
Table 15 high concentration pollutant inlet and outlet flue gas detection data of 20 ton/hr
Example 11: sodium glycinate-glycine solution 168 hour tracking monitor 45 ton/hour coal-fired boiler flue gas purification monitoring statistical average result
The conditions and results associated with a follow-up rated deep clean-up of a portion of the flue gas from a 45t coal-fired boiler using the sodium glycinate-glycine process (liquid concentration with flue gas treatment work in example 10) for 168 hours were as follows:
The tower diameter is 2m, the tower height is 20m, the flue gas inlet flow (standard dry) is 46365Nm 3/h, the liquid spray amount is 45m 3/h, the pH range of the circulating sodium glycinate-glycine flue gas treatment working solution is 6.0-8.0, and the ammonia spraying amount is 17kg/h. The flue gas temperature was 112℃with an inlet oxygen content of 9.3%, an inlet SO 2 average concentration of 166.2mg/Nm 3, an inlet NOx average concentration of 41.3mg/Nm 3, a dust concentration of 30.6mg/Nm 3, an outlet flue gas outlet flow 30750Nm 3/h, a temperature of 46℃with an oxygen content of 8.5%, an outlet sulfur dioxide concentration of 0.7mg/Nm 3, a nitrogen oxide content of 24.6mg/Nm 3, and a dust concentration of 6.5mg/Nm 3.
Claims (6)
1. A process for flue gas catalytic-free ammonia injection primary denitration, deep dedusting, desulfurization and denitration and ammonia capture of an amino acid-amino acid salt circulating liquid is characterized in that: directly spraying ammonia into high-temperature flue gas to perform catalytic-free denitration, using an aqueous solution containing amino acid and amino acid soluble salt as a flue gas treatment working solution to perform deep purification to obtain an absorption solution, recycling and recycling the absorption solution, and performing spray washing on the flue gas after deep purification to realize flue gas re-purification; wherein,
The aqueous solution of amino acid and amino acid soluble salt is sodium glycinate-glycine mixed aqueous solution or calcium glycinate-glycine aqueous solution;
the absorption liquid is recycled by adopting calcium glycinate solution to treat the absorption liquid.
2. The process according to claim 1, wherein the molar ratio of sodium glycinate to glycine in the aqueous sodium glycinate-glycine mixed solution is 1:0.1-10.0.
3. The process according to claim 2, wherein the molar ratio of sodium glycinate to glycine in the aqueous sodium glycinate-glycine mixed solution is 1:0.2-5.0.
4. A process according to any one of claims 1-3, characterized in that the spray scrubbing is a continuous spray scrubbing of the packing layer and flue gas with make-up water at the top of the wire mesh packing tower.
5. Use of the process according to any of claims 1-4, characterized in that the process according to any of claims 1-4 is used for the conventionally required dust removal desulfurization denitration or upgrading of flue gases to ultra low emission purification equipment.
6. The method according to claim 5, wherein the device is a device applying high-efficiency cyclone purification technology or is a device performing high-efficiency deep dust removal, desulfurization and denitrification through gas-liquid film mass transfer with a wire mesh spherical packed tower.
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| WO2014127980A1 (en) * | 2013-02-21 | 2014-08-28 | Siemens Aktiengesellschaft | Process and apparatus for processing a gas stream and especially for processing a flue gas stream |
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