CN113117512A - Wet flue gas desulfurization solid synergist and preparation method thereof - Google Patents
Wet flue gas desulfurization solid synergist and preparation method thereof Download PDFInfo
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- CN113117512A CN113117512A CN202110448572.6A CN202110448572A CN113117512A CN 113117512 A CN113117512 A CN 113117512A CN 202110448572 A CN202110448572 A CN 202110448572A CN 113117512 A CN113117512 A CN 113117512A
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- flue gas
- gas desulfurization
- wet flue
- synergist
- solid synergist
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 72
- 230000023556 desulfurization Effects 0.000 title claims abstract description 72
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003546 flue gas Substances 0.000 title claims abstract description 49
- 239000007787 solid Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims abstract description 17
- 230000001070 adhesive effect Effects 0.000 claims abstract description 17
- 238000005507 spraying Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000006172 buffering agent Substances 0.000 claims abstract description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 25
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 25
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 18
- 229940069328 povidone Drugs 0.000 claims description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 6
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 238000000889 atomisation Methods 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011575 calcium Substances 0.000 abstract description 5
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000002250 absorbent Substances 0.000 abstract description 4
- 230000002745 absorbent Effects 0.000 abstract description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 8
- 239000010440 gypsum Substances 0.000 description 7
- 229910052602 gypsum Inorganic materials 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 238000005550 wet granulation Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000019643 salty taste Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 235000019654 spicy taste Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 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
- B01D53/81—Solid phase processes
-
- 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
- B01D53/508—Sulfur oxides by treating the gases with solids
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention provides a solid synergist for wet flue gas desulfurization and a preparation method thereof, wherein the solid synergist comprises the following components in percentage by weight: 60% -80% of buffering agent, 10% -25% of surfactant, 10% -20% of inorganic salt and 2% -8% of adhesive. The preparation method of the solid synergist for wet flue gas desulfurization comprises the steps of dissolving a buffering agent and a binder in water, and uniformly stirring to obtain a binder solution for later use; adding a surfactant and inorganic salt into a fluidized bed for preheating, spraying the adhesive solution when the temperature of the surfactant and the inorganic salt reaches 35-50 ℃, and drying after spraying to obtain dry particles; and (4) finishing the dry particles. The use method of the wet flue gas desulfurization solid synergist comprises the step of adding the wet flue gas desulfurization solid synergist with the concentration of 20-50 mg/L into a calcium absorbent. The synergist provided by the invention has the advantages of quick effect, low consumption, simple formula, high desulfurization efficiency, simple preparation method and good process reproducibility, and the components in the produced product are uniformly distributed.
Description
Technical Field
The invention relates to the technical field of flue gas desulfurization, in particular to a solid synergist for wet flue gas desulfurization and a preparation method thereof.
Background
Sulfur dioxide has great harm to the environment, can cause acid rain and acid mist, has a corrosive effect on the environment, and also has a carcinogenic effect on human bodies. In recent years, the haze in coastal industrial areas is seriously damaged, and one of main components of the haze is sulfur dioxide.
With the increasing of the force of sulfur dioxide emission reduction policy in China and the popularization and application of various desulfurization technologies in coal-fired power plants, the sulfur dioxide emission is effectively controlled. However, in the actual operation process of the power plant, various unstable factors such as large coal quality fluctuation, uneven coal types, variation of power generation load of the boiler, unstable quality of the calcium absorbent and the like are faced, and a great interference effect is achieved on the operation of the desulfurizing tower.
After the issuance of new environmental regulations, many power plants are difficult to reach the maximum standard and cannot well meet the emission control of sulfur dioxide, so that the power plants are required to upgrade and modify the existing desulfurization system aiming at a new emission limit value, which means expensive modification cost and huge loss of shutdown. Therefore, the method improves the desulfurization efficiency on the basis of the traditional desulfurization system, and becomes the first choice of enterprises. The desulfurization additive is the preferred scheme under the condition, and compared with a modified device, the desulfurization additive has the advantages of low cost and wide applicability.
At present, additives for limestone wet desulphurization are mainly classified into three types: inorganic additives with high efficiency but large dosage, organic additives with slow effect but small dosage, and composite additives with the advantages of the two.
For example, the Chinese patent application publication No. CN 105289269A of 'a desulfurization synergist for a wet flue gas desulfurization system of a thermal power plant' discloses a desulfurization synergist for a wet flue gas desulfurization system of a thermal power plant, which comprises the following components: the composite material comprises a surfactant, a cosolvent, a PH buffer and an oxidation catalyst, wherein the preferable mass percentage is as follows: 40-60% of surfactant, 20-40% of cosolvent, 5-15% of PH buffer and 2-5% of oxidation catalyst. The desulfurization synergist is added into a calcium absorbent, and the use concentration is 150 mg/L-600 mg/L. The desulfurization synergist can promote the dissolution balance of the calcium absorbent to move to the positive direction and improve the solubility of calcium; the pH value of a gas-liquid interface is stabilized, and the dissolving speed of sulfur dioxide is increased; the oxidation speed is improved, and the generation of gypsum is accelerated; the circulation amount of the absorption slurry is reduced, the consumption of the absorption slurry is reduced, and the effects of saving energy, reducing consumption, lowering cost and improving efficiency are achieved. However, the novel compound desulfurization synergist has a complex formula and needs to be used in a high dosage.
Also for example, the Chinese patent application publication No. CN 104722205A of "a limestone-gypsum wet flue gas desulfurization synergist" discloses a limestone-gypsum wet flue gas desulfurization synergist, which consists of the following components: sebacic acid, ferric oxide and sodium hexametaphosphate. Wherein the content of the sebacic acid is 80-90%. Wherein the content of ferric oxide is 5-15%. Wherein the content of sodium hexametaphosphate is 3-8%. The optimal use concentration is 1.2-1.5 g/L. The desulfurization synergist of the invention is beneficial to improving the dissolution rate of limestone and the absorption rate of SO 2; meanwhile, the metal oxide with catalytic oxidation can improve the oxidation rate of the calcium sulfite; the dispersing agent can ensure the dispersibility of solid particles in the slurry and reduce the equipment blockage caused by the precipitation of the solid particles. The synergist of the invention can improve the wet desulphurization efficiency by 5-10%, reduce the consumption of limestone and improve the reliability of equipment operation. However, analysis shows that the amount of the synergist in the invention is extremely high, and a new pollutant, namely phosphorus, is introduced.
Disclosure of Invention
The invention provides a solid synergist for wet flue gas desulfurization and a preparation method thereof for solving the technical problems, wherein a buffer agent and an adhesive are dissolved in water to prepare an adhesive solution; adding a surfactant and inorganic salt into a fluidized bed for preheating, spraying the adhesive solution after the preset material temperature is reached, and drying after spraying to obtain dry particles; and finally, the obtained dry particles are granulated, so that the effects of simple preparation method, good process reproducibility and uniform distribution of all components in the produced product are achieved.
The invention relates to a solid synergist for wet flue gas desulfurization and a preparation method thereof, and the technical scheme is as follows:
a solid synergist for wet flue gas desulfurization comprises the following components in percentage by weight: 60% -80% of buffering agent, 10% -25% of surfactant, 10% -20% of inorganic salt and 2% -8% of adhesive.
Preferably in any one of the above embodiments, the buffer comprises one or more of citric acid, sodium citrate, succinic acid, adipic acid, tartaric acid, ascorbic acid, benzoic acid, malic acid.
In any of the above embodiments, preferably, the surfactant comprises one or more of stearic acid, sodium dodecylbenzenesulfonate, and sodium dioctyl sulfosuccinate.
In any of the above schemes, preferably, the inorganic salt is one or more of sodium chloride, potassium carbonate, potassium oxalate, magnesium sulfate, and calcium sulfate.
In any of the above embodiments, preferably, the binder is one or more of pregelatinized gelatin, povidone, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, powdered sugar, starch slurry, and gelatin.
In any of the above aspects, preferably, the binder is povidone.
Preferably in any of the above embodiments, the binder is povidone K29/32.
In any of the above schemes, it is preferable that the D90 of the wet flue gas desulfurization solid synergist is less than or equal to 100 μm. Said "D90"means the particle size corresponding to 90% of the cumulative particle size distribution of a sample. Its physical meaning is that 90% of the particles have a particle size smaller than that of the particles, e.g. "D90Not more than 100 μm "means" 90% of particles not more than 100. mu.m ".
A preparation method of a wet flue gas desulfurization solid synergist comprises the following steps:
dissolving a buffering agent and an adhesive in water, and uniformly stirring to obtain an adhesive solution for later use;
adding a surfactant and an inorganic salt into a fluidized bed for preheating, and spraying the adhesive solution when the temperature of the surfactant and the inorganic salt reaches 35-50 ℃;
after the spraying is finished, drying to obtain dry particles;
and (4) finishing the dry particles.
In any of the above embodiments, it is preferable that the binder solution is sprayed at an atomization pressure of 0.5bar to 2.0bar and a spray velocity of 3.0g/min to 20.0 g/min.
The invention has the beneficial effects that:
1. the solid synergist for wet flue gas desulfurization provided by the invention has the advantages of small particle size, more gaps and large specific surface area, and can greatly improve the desulfurization efficiency, so that the dosage of the synergist is less.
2. The solid synergist for wet flue gas desulfurization provided by the invention has the advantages of quick effect, low consumption, simple formula, overall reduced cost and certain economic benefit.
3. The preparation method of the wet flue gas desulfurization solid synergist provided by the invention adopts a wet granulation technology to prepare the synergist, the method is simple, the process reproducibility is good, and the components in the produced product are uniformly distributed.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the following further discloses some non-limiting examples to further explain the present invention in detail.
In the examples described below, all temperatures are given in degrees Celsius unless otherwise indicated. The reagents used are either commercially available or can be prepared by the methods described herein.
Example 1
A solid synergist for wet flue gas desulfurization is prepared from the following raw materials in percentage by weight:
the preparation method of the wet flue gas desulfurization solid synergist comprises the following steps:
(1) weighing water according to the concentration of 20 percent (g/ml) of povidone, sequentially adding 600g of sodium citrate and 80g of povidone into the water, and stirring to dissolve the sodium citrate and the povidone to obtain an adhesive solution for later use;
(2) 220g of sodium dioctyl sulfosuccinate and 100g of magnesium sulfate were added to the fluidized bed and preheated, and spraying of the binder solution obtained in step (1) was started when the material temperature reached 42 ℃.
(3) And (5) after the liquid spraying is finished. Drying until LOD and acetic acid residue of the product are lower than quality standard to obtain dry granules.
(4) And (4) granulating the obtained dry particles by using a granulator to obtain the target product.
The raw material povidone used in this example is polyvinylpyrrolidone (PVP), which is a chemical name, and is obtained by bulk polymerization, solution polymerization, or the like using vinyl pyrrolidone (NVP) as a monomer as a raw material. PVP is classified into four grades based on its average molecular weight, which is conventionally represented by the K value, with different K values representing the respective PVP average molecular weight ranges. The K value is actually a characteristic value related to the relative viscosity of the aqueous solution of PVP, which in turn is a physical quantity related to the molecular weight of the high polymer, and thus the K value can be used to characterize the average molecular weight of PVP. In general, the larger the K value, the higher the viscosity, and the stronger the adhesiveness. PVP is used as a synthetic water-soluble polymer compound, has the general properties of the water-soluble polymer compound, and has the advantages of colloid protection effect, film-forming property, cohesiveness, hygroscopicity, solubilization or condensation effect, excellent solubility and physiological compatibility, and the PVP is soluble in water and most of organic solvents, and has low toxicity and good physiological compatibility.
Example 2
A solid synergist for wet flue gas desulfurization is prepared from the following raw materials in percentage by weight:
the preparation method of the wet flue gas desulfurization solid synergist comprises the following steps:
(1) weighing water according to the concentration of the povidone of 22.5 percent (g/ml), sequentially adding 780g of adipic acid and 20g of povidone into the water, and stirring to dissolve the materials to obtain an adhesive solution for later use;
(2) 100g of sodium dioctyl sulfosuccinate and 100g of calcium sulfate were introduced into the fluidized bed and preheated, and spraying of the binder solution obtained in step (1) was started when the batch temperature reached 42 ℃.
(3) And (5) after the liquid spraying is finished. Drying until LOD and acetic acid residue of the product are lower than quality standard to obtain dry granules.
(4) And (4) granulating the obtained dry particles by using a granulator to obtain the target product.
The adipic acid used as a raw material in this embodiment is also referred to as adipic acid, and is an important organic dibasic acid, which can undergo a salt formation reaction, an esterification reaction, an amidation reaction, and the like, and can be polycondensed with diamine or diol to form a high-molecular polymer, and the like.
Example 3
A solid synergist for wet flue gas desulfurization is prepared from the following raw materials in percentage by weight:
the preparation method of the wet flue gas desulfurization solid synergist comprises the following steps:
(1) weighing glacial acetic acid according to the concentration of 20% (g/ml) of povidone, sequentially adding 600g of adipic acid and 50g of povidone into the glacial acetic acid, and stirring to dissolve the mixture to obtain an adhesive solution for later use;
(2) 250g of sodium dioctyl sulfosuccinate and 100g of calcium sulfate were introduced into the fluidized bed and preheated, and spraying of the binder solution obtained in step (1) was started when the batch temperature reached 42 ℃.
(3) And (5) after the liquid spraying is finished. Drying until LOD and acetic acid residue of the product are lower than quality standard to obtain dry granules.
(4) And (4) granulating the obtained dry particles by using a granulator to obtain the target product.
The calcium carbonate used as a raw material in this example was white monoclinic crystal or crystalline powder, and had no odor and hygroscopicity. Losing 1 molecule of crystal water at 128 ℃ and losing all water at 163 ℃. Dissolving in acid, sodium thiosulfate and ammonium salt solution, and dissolving in 400 parts
Water, which dissolves less in hot water, dissolves very slowly in glycerol, and is practically insoluble in ethanol and most organic solvents. The relative density was 2.32. Has irritation.
The solid synergist for wet flue gas desulfurization provided by the embodiment has the following technical effects:
1. the wet flue gas desulfurization solid synergist provided by the embodiment has the advantages of small particle size, more gaps and large specific surface area, and can greatly improve the desulfurization efficiency, so that the dosage of the synergist is less.
2. The solid synergist for wet flue gas desulfurization provided by the embodiment has the advantages of quick effect, low consumption and simple formula, reduces the cost on the whole and has certain economic benefit.
3. The preparation method of the solid synergist for wet flue gas desulfurization provided by the embodiment adopts a wet granulation technology to prepare the synergist, the method is simple, the process reproducibility is good, and the components in the produced product are uniformly distributed.
Example 4
A solid synergist for wet flue gas desulfurization is prepared from the following raw materials in percentage by weight:
the preparation method of the wet flue gas desulfurization solid synergist comprises the following steps:
(1) weighing water according to the concentration of 20 percent (g/ml) of povidone, sequentially adding 600g of sodium citrate and 50g of povidone into the water, and stirring to dissolve the sodium citrate and the povidone to obtain an adhesive solution for later use;
(2) 150g of sodium dioctyl sulfosuccinate and 200g of magnesium sulfate were added to the fluidized bed and preheated, and spraying of the binder solution obtained in step (1) was started when the material temperature reached 42 ℃.
(3) And (5) after the liquid spraying is finished. Drying until LOD and acetic acid residue of the product are lower than quality standard to obtain dry granules.
(4) And (4) granulating the obtained dry particles by using a granulator to obtain the target product.
The raw material sodium citrate used in this example, also known as sodium citrate, is an organic compound and is white to colorless crystal in appearance. No odor, and cool, salty and spicy taste. Stable at normal temperature and in air, has slight solubility in humid air, and generates weathering phenomenon in hot air. Heating to 150 ℃ lost the water of crystallization. Is easily soluble in water, soluble in glycerol, and insoluble in alcohols and other organic solvents, and can be decomposed by overheating, deliquesced slightly in humid environment, and weathered slightly in hot air, and the pH value of the solution is about 8.
The desulfurization synergy research results are as follows:
at an inlet sulfur dioxide concentration of>2000mg/m3The desulfurization rates of limestone-gypsum wet flue gas desulfurization systems without the addition of the synergist of the present invention and systems with the addition of the synergist described in examples 1-4 of the present invention are shown in the following table.
Table 1: desulfurization rate comparison data table
It can be seen from the data in the table that, after the solid synergist for wet flue gas desulfurization obtained in examples 1-4 is added into a limestone-gypsum wet flue gas desulfurization system according to 20mg/L, the sulfur dioxide concentration at the outlet is respectively reduced from 2689 to 53.78, 2429 to 73, 2097 to 83.88, and 2865 to 86, and the desulfurization rates are respectively 98%, 97%, 96%, and 97%, whereas the desulfurization rate is only 82% without adding the invention into the limestone-gypsum wet flue gas desulfurization system, it can be obviously found that the desulfurization rate is significantly improved after adding the synergist of the invention, and all can reach the latest national emission standard, the sulfur dioxide concentration at the outlet of the solid synergist for wet flue gas desulfurization obtained in example 3 with 50mg/L added into the limestone-gypsum wet flue gas desulfurization system is reduced from 2827 to 28.27, and the desulfurization efficiency is 99%, it can be seen that within a suitable range, the desulfurization rate is increased with the increase in the amount of the enhancer of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.
In the context of the present invention, all numbers disclosed herein are approximate values, regardless of whether the word "about" or "approximately" is used. There may be differences below 10% in the value of each number or reasonably considered by those skilled in the art, such as differences of 1%, 2%, 3%, 4% or 5%.
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The solid synergist for wet flue gas desulfurization is characterized by comprising the following components in percentage by weight: 60% -80% of buffering agent, 10% -25% of surfactant, 10% -20% of inorganic salt and 2% -8% of adhesive.
2. The wet flue gas desulfurization solid synergist according to claim 1, wherein the buffer comprises one or more of citric acid, sodium citrate, succinic acid, adipic acid, tartaric acid, ascorbic acid, benzoic acid, and malic acid.
3. The wet flue gas desulfurization solid synergist according to claim 2, wherein the surfactant comprises one or more of stearic acid, sodium dodecylbenzene sulfonate, and sodium dioctyl sulfosuccinate.
4. The wet flue gas desulfurization solid synergist according to claim 3, wherein the inorganic salt is one or more of sodium chloride, potassium carbonate, potassium oxalate, magnesium sulfate, and calcium sulfate.
5. The wet flue gas desulfurization solid synergist according to claim 4, wherein the binder is one or more of pregelatinized gelatin, povidone, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, powdered sugar, starch slurry, and gelatin.
6. The wet flue gas desulfurization solid synergist according to claim 5, wherein the binder is povidone.
7. The wet flue gas desulfurization solid synergist according to claim 6, wherein the binder is povidone K29/32.
8. The wet flue gas desulfurization solid synergist according to claim 7, wherein D of the wet flue gas desulfurization solid synergist is90≤100μm。
9. The method for preparing the solid synergist for wet flue gas desulfurization according to any one of claims 1 to 8, comprising the steps of:
dissolving a buffering agent and an adhesive in water, and uniformly stirring to obtain an adhesive solution for later use;
adding a surfactant and an inorganic salt into a fluidized bed for preheating, and spraying the adhesive solution when the temperature of the surfactant and the inorganic salt reaches 35-50 ℃;
after the spraying is finished, drying to obtain dry particles;
and (4) finishing the dry particles.
10. The method for preparing the solid synergist for wet flue gas desulfurization according to claim 9, wherein the binder solution is sprayed at an atomization pressure of 0.5bar to 2.0bar and a spraying speed of 3.0g/min to 20.0 g/min.
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