CN116688745B - Combined desulfurizing agent and method for improving desulfurization standard of garbage incineration system - Google Patents
Combined desulfurizing agent and method for improving desulfurization standard of garbage incineration system Download PDFInfo
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- CN116688745B CN116688745B CN202310990619.0A CN202310990619A CN116688745B CN 116688745 B CN116688745 B CN 116688745B CN 202310990619 A CN202310990619 A CN 202310990619A CN 116688745 B CN116688745 B CN 116688745B
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 72
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 53
- 230000023556 desulfurization Effects 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 64
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 60
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 60
- 239000004571 lime Substances 0.000 claims abstract description 60
- 239000002002 slurry Substances 0.000 claims abstract description 59
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 27
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011787 zinc oxide Substances 0.000 claims abstract description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 56
- 239000004094 surface-active agent Substances 0.000 claims description 50
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 22
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 21
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 21
- 239000012046 mixed solvent Substances 0.000 claims description 21
- 239000004246 zinc acetate Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 14
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 14
- -1 5-bromopentanal glycol acetal Chemical class 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- DBLXOVFQHHSKRC-UHFFFAOYSA-N ethanesulfonic acid;2-piperazin-1-ylethanol Chemical compound CCS(O)(=O)=O.OCCN1CCNCC1 DBLXOVFQHHSKRC-UHFFFAOYSA-N 0.000 claims description 13
- 150000007524 organic acids Chemical class 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 11
- 229960000892 attapulgite Drugs 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- 229910052625 palygorskite Inorganic materials 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- JUXXCHAGQCBNTI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylpropane-1,2-diamine Chemical compound CN(C)C(C)CN(C)C JUXXCHAGQCBNTI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 235000011044 succinic acid Nutrition 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims 2
- 238000005886 esterification reaction Methods 0.000 claims 2
- 238000005266 casting Methods 0.000 claims 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003546 flue gas Substances 0.000 abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011593 sulfur Substances 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 238000011426 transformation method Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000002407 reforming Methods 0.000 abstract description 2
- 230000003381 solubilizing effect Effects 0.000 abstract description 2
- 235000015165 citric acid Nutrition 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 15
- 235000019738 Limestone Nutrition 0.000 description 13
- 239000006028 limestone Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 235000011116 calcium hydroxide Nutrition 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 description 3
- 238000007405 data analysis Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- BPINJMQATUWTID-UHFFFAOYSA-N 3,3-dimethylpentane-2,2-diamine Chemical compound CCC(C)(C)C(C)(N)N BPINJMQATUWTID-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000004056 waste incineration 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
- 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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20715—Zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20792—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
Abstract
The application discloses a combined desulfurizing agent and a method for desulfurizing, upgrading and reforming a garbage incineration system, and relates to the technical field of adsorbents and catalysts. The combined desulfurizing agent comprises a calcium base and a composite metal oxide with a catalytic reaction function, wherein the composite metal oxide is granular, and the grain diameter is 3-6 mm; the above composite metal oxide includes zinc oxide, zirconium oxide and cerium oxide. The application also discloses a desulfurization and upgrading transformation method of the garbage incineration system, which comprises the following steps: adding the combined desulfurizing agent in a high-temperature section of the garbage incineration system; and simultaneously, adding a solubilizing reagent into the lime slurry preparation tank body at the desulfurization reaction tower part. The combined desulfurizing agent provided by the application has better desulfurizing capability, and the sulfur capacity is obviously improved; the method applied to desulfurization and standard improvement of the garbage incineration system can further improve the desulfurization effect of the method and reduce the initial value of sulfur dioxide in the flue gas.
Description
Technical Field
The application belongs to the technical field of adsorbents and catalysts, and particularly relates to a combined desulfurizing agent and a method for desulfurizing, upgrading and reforming a garbage incineration system.
Background
SO in original flue gas of garbage incineration power generation facility 2 Is typically present in an amount of 200-800mg/Nm 3 Typical HCl content is 600-1200mg/Nm 3 . Considering that HCl is relatively easy to remove, while SO 2 Is difficult to remove and SO 2 The content is also an index for controlling the total amount of the atmospheric pollutants, SO that SO is highly valued by garbage incineration power generation enterprises 2 Is controlled by the emission reduction control of the engine. At present, the SO of the garbage incineration power generation facility is regulated in the domestic garbage incineration pollution control Standard (GB 18485-2014) 2 The hourly average limit of the discharge was 100mg/Nm 3 . However, coastal and economically developed areas have developed more stringent SO due to total emissions control 2 And emission reduction is required.
At present, most household garbage incineration power generation enterprises adopt semi-dryThe denitration agent used in the desulfurization process of the method and the dry method is mainly slaked lime (slaked lime, main component Ca (OH)) 2 ). However, in the actual operation process, the conventional method has certain drawbacks, mainly listed as follows:
1. the fly ash amount is large, the ash yield per ton of garbage in the incineration process of the existing grate furnace is about 3%, and the problems of technology and cost of disposal along with fly ash landfill are more remarkable. The problem that the enterprise urgently solves is solved to low ash yield. However, excessive dosing of agents to fly ash by semi-dry and dry desulfurization can result in significant increases in fly ash levels. Increasing the end-of-business disposal costs.
2. The flue gas temperature is low, the existing semi-dry method is mainly, the dry method is used as an auxiliary desulfurization mode, the dependency on the semi-dry method is serious, and the problem of exceeding standard of sulfides in the flue gas is mainly adjusted by the semi-dry method lime slurry adding mode. The method can cause obvious reduction of the temperature of the flue gas in a short time, and the reduction of the temperature of the flue gas can cause the occurrence of systematic problems such as insufficient cyclic utilization of the heat energy of the flue gas tail gas, poor subsequent SCR denitration effect, poor white removal treatment of the flue gas tail gas and the like.
Disclosure of Invention
The application aims to provide a combined desulfurizing agent and a method for improving desulfurization of a garbage incineration system, wherein the combined desulfurizing agent has better desulfurization capacity and obviously improves sulfur capacity; the method applied to desulfurization and standard improvement of the garbage incineration system can further improve the desulfurization effect of the method and reduce the initial value of sulfur dioxide in the flue gas.
The technical scheme adopted by the application for achieving the purpose is as follows:
a combined desulfurizing agent comprises a calcium-based composite metal oxide with a catalytic reaction function, wherein the calcium-based composite metal oxide is granular, and the grain diameter is 3-6 mm;
the above composite metal oxide includes zinc oxide, zirconium oxide and cerium oxide. The application provides a combined desulfurizing agent, which shows more excellent desulfurizing activity by calcium-based composite metal oxide with catalytic reaction. The application adds the surfactant prepared by 5-bromopentanal glycol acetal in the preparation process of the composite metal oxide, and the same asWhen the combined desulfurizing agent is applied to desulfurization treatment of a garbage incineration system, the desulfurization effect of the system can be remarkably enhanced, and the concentration of sulfur dioxide at an outlet is obviously reduced; and NO x The total emission concentration is also reduced. The reason for this may be that the surfactant prepared from 5-bromopentanal glycol acetal exhibits more excellent performance, and modified calcium hydroxide is added to the composite metal oxide, so that a large number of reaction sites are provided for desulfurization by changing the physical structure of the desulfurizing agent, increasing the specific surface area; and the pore structure of the desulfurizing agent can be improved, which is beneficial to SO 2 The equal gas enters into the inner pore canal of the desulfurizer particles, thereby improving the desulfurization capacity; meanwhile, under the action of the active components of the catalyst, the utilization rate of the active components of the desulfurizing agent is high, and the activity and the stability can be kept high.
The application also discloses a preparation method of the combined desulfurizing agent, which comprises the following steps:
mixing zinc acetate, cerous nitrate and zirconyl nitrate, adding distilled water, glycol and acetone mixed solvent for dissolution, adding urea and surfactant, controlling the pressure to be 1.5-2.5 MPa, preserving heat for 10-15 h at 220-250 ℃, filtering and drying to obtain a composite metal oxide;
and adding modified calcium hydroxide and attapulgite into the composite metal oxide, adding water, uniformly mixing, kneading, forming, drying, and roasting at 400-600 ℃ for 1-3 hours to obtain the combined desulfurizing agent.
Further specifically, the preparation method of the combined desulfurizing agent comprises the following steps:
mixing zinc acetate, cerous nitrate and zirconyl nitrate, adding distilled water, glycol and acetone mixed solvent for dissolution, continuously stirring at high speed for 1h for uniform mixing, adding urea for ultrasonic mixing for 10-20 min, then adding surfactant, continuously stirring for 15-25 min, placing in a high-pressure reaction kettle, sealing, controlling the pressure to be 1.5-2.5 MPa, preserving heat for 10-15 h at 220-250 ℃, cooling, taking out, filtering, and drying to obtain the composite metal oxide;
and adding modified calcium hydroxide and attapulgite into the composite metal oxide, adding water, uniformly mixing, kneading, forming into particles, drying at 110-120 ℃ for 8-12 h, and roasting at 400-600 ℃ for 1-3 h to obtain the combined desulfurizing agent.
Further, the molar ratio of zinc acetate to cerium nitrate to zirconyl nitrate is 1:2-4:0.5-1.5; the volume ratio of distilled water to glycol to acetone is 1:1.5-2.5:0.8-1.2; the dosage ratio of the zinc acetate to the mixed solvent is 0.045-0.12 mol:1L; the molar ratio of urea to the mixture of zinc acetate, cerium nitrate and zirconyl nitrate is 0.02-0.08:1; the molar ratio of the surfactant to the urea is 1.2-2:1.
Further, the mass ratio of the composite metal oxide to the modified calcium hydroxide to the attapulgite is 1:4-6:0.6-1.
Further, the surfactant includes quaternary ammonium salt surfactant.
Further, the quaternary ammonium salt surfactant comprises tetradecyl trimethyl ammonium bromide or hexadecyl trimethyl ammonium bromide.
Further preferably, the quaternary ammonium salt surfactant further comprises a product of a chemical reaction of 5-bromopentanal ethylene glycol acetal with tetramethylpropanediamine.
The application also discloses a preparation method of the surfactant, which comprises the following steps:
and adding tetramethyl propylene diamine into 5-bromopentanal glycol acetal, adding ethanol, carrying out reflux reaction at 80-85 ℃ for 42-48 h, then carrying out rotary evaporation, adding acetone at 0-4 ℃ for extraction, washing the extract with acetone, and drying to obtain the surfactant.
Further, the molar ratio of the 5-bromopentanal glycol acetal to the tetramethyl-propylene diamine is 2-2.4:1; the dosage ratio of the 5-bromovaleraldehyde glycol acetal to the ethanol is 0.2-0.3 g:1mL.
Further, the modified calcium hydroxide includes a product of surfactant modified calcium hydroxide.
Preparing the modified calcium hydroxide:
and (3) adding a surfactant and a proper amount of water into the sieved calcium hydroxide, mechanically stirring and heating to paste, and then drying and grinding the paste at 120-125 ℃ to obtain the modified calcium hydroxide.
Further, the mass ratio of the surfactant to the calcium hydroxide is 0.05-0.08:1.
A method for desulfurizing and upgrading a garbage incineration system, comprising the following steps: adding the combined desulfurizing agent in a high-temperature section of the garbage incineration system; and simultaneously, adding a solubilizing reagent into the lime slurry preparation tank body at the desulfurization reaction tower part.
It should be noted that:
in the high temperature section: adding a combined desulfurizing agent in the range of 850-1050 ℃, and spraying the desulfurizing agent to the high-temperature section of the garbage incinerator in a pneumatic conveying mode provided by a Roots blower and the like; within this addition amount range, the initial value of sulfur dioxide in the furnace can be reduced by 30% in general;
in the desulfurization reaction tower part: a solubilizer is required to be added into the lime slurry preparation tank body, so that the concentration of the lime slurry is improved; namely, the preparation of lime slurry comprises the following steps:
adding deionized water into limestone, mixing, adding solubilizer, and stirring to obtain lime slurry.
Further, the solid-to-liquid ratio of the limestone to the deionized water is 3-5 mg/1 mL; the addition amount of the solubilizer is 400-600 mg/L lime slurry.
It is further noted that the solubilizing agent includes an organic acid and a surfactant; the molar ratio of the two is 1:0.1-0.3.
Further, the organic acid includes citric acid, benzoic acid, adipic acid, or succinic acid.
Further, the addition amount of the combined desulfurizing agent is 3-6 kg/t of garbage.
More preferably, the organic acid further comprises a citric acid derivative.
The citric acid derivative includes a product of hydroxyethylidene diphosphonate modified citric acid and/or a product of 4-hydroxyethylpiperazine ethanesulfonate modified citric acid. The application adopts hydroxy ethylidene diphosphonic acid or 4-hydroxyethyl piperazine ethane sulfonic acid to react with citric acid to prepare the citric acid derivative, and the citric acid derivative is added into a solubilizer as organic acid and then applied to lime slurry, thus effectively enhancing the solubility of limestoneThe obtained lime slurry has better SO 2 Absorption effect, SO 2 The absorption rate is obviously improved; the sulfur dioxide is applied to desulfurization treatment of a garbage incineration system, and is compounded with a combined desulfurizing agent, so that the desulfurization effect of the system can be obviously enhanced, and the concentration of sulfur dioxide at an outlet is obviously reduced; and NO x The total emission concentration is also reduced. And the addition of the solubilizer can effectively relieve the layering speed of lime slurry and water in the preparation process and reduce the viscosity of lime slurry suspension, so that the problems of pipeline blockage, material layering, lime deposition, jet orifice blockage and the like cannot occur in the process of preparing higher concentration of lime slurry.
The preparation method of the citric acid derivative comprises the following steps: mixing hydroxyethylidene diphosphonic acid or 4-hydroxyethylpiperazine ethanesulfonic acid with citric acid, and reacting to obtain citric acid derivative.
Specifically, the preparation method of the citric acid derivative comprises the following steps:
mixing citric acid with hydroxyethylidene diphosphonic acid or 4-hydroxyethylpiperazine ethanesulfonic acid, adding benzenesulfonic acid and toluene, dropwise adding phosphoric acid, heating and refluxing, carrying out water diversion through a water diversion device, carrying out reduced pressure distillation after reacting for 5-8 hours, cooling to room temperature, dropwise adding saturated sodium bicarbonate solution until the pH value of the system is neutral, extracting by adopting anhydrous diethyl ether, washing for 4-6 times by using saturated saline water, drying by using anhydrous sodium sulfate, and carrying out reduced pressure distillation to collect fractions at 162-163 ℃ to obtain the citric acid derivative.
Further, the molar ratio of the citric acid to the hydroxyethylidene diphosphonic acid or the 4-hydroxyethylpiperazine ethanesulfonic acid is 1:3-3.5; the adding amount of the benzenesulfonic acid is 0.4-0.6wt% of the citric acid; the solid-liquid ratio of the citric acid to the toluene is 0.4-0.6 g:1mL; the dosage ratio of phosphoric acid to citric acid is 1 drop: 2-3 g.
It is a further object of the present application to disclose the use of the above-mentioned combined desulfurization agent for enhancing the desulfurization and/or denitrification capacity of a waste incineration system.
The application also discloses the application of the prepared surfactant in enhancing the sulfur capacity of the combined desulfurizing agent.
The application also discloses the application of the prepared solubilizer in enhancing the dissolution performance of limestone.
The application also discloses the application of the prepared solubilizer in enhancing the desulfurization capacity of lime slurry.
Compared with the prior art, the application has the following beneficial effects:
according to the combined desulfurizing agent provided by the application, the calcium base is assisted by the composite metal oxide with the catalytic reaction function, and the surfactant is added, so that the combined desulfurizing agent prepared under the synergistic effect has stronger desulfurizing efficiency, the sulfur capacity is obviously improved, the combined desulfurizing agent is applied to the desulfurization treatment of a garbage incineration system, the desulfurizing effect of the system can be obviously enhanced, and the concentration of sulfur dioxide at an outlet is obviously reduced; and NO x The total emission concentration is also reduced. In addition, the citric acid derivative is prepared by reacting the hydroxyethylidene diphosphonic acid or the 4-hydroxyethylpiperazine ethanesulfonic acid with citric acid, and is added into the solubilizer as organic acid and then applied to lime slurry, so that the dissolution performance of lime slurry can be effectively enhanced, the layering speed of lime slurry and water in the preparation process can be effectively relieved, and the viscosity of lime slurry suspension can be reduced; the obtained lime slurry has better SO 2 The absorption effect is compounded with the combined desulfurizing agent, the desulfurizing effect of the system can be obviously enhanced, and NO is treated x Also has certain removing effect. The application can ensure that the tail flue gas temperature is increased by about 15-20 ℃ and reduce corrosion under the premise of controlling the reduction of the sulfur dioxide emission value through the use of the combined desulfurizing agent and lime slurry solubilizing agent.
Therefore, the application provides a combined desulfurizing agent and a method for improving desulfurization of a garbage incineration system, wherein the combined desulfurizing agent has better desulfurization capacity and obviously improves sulfur capacity; the method applied to desulfurization and standard improvement of the garbage incineration system can further improve the desulfurization effect of the method and reduce the initial value of sulfur dioxide in the flue gas.
Drawings
FIG. 1 is a schematic flow chart of a desulfurization method in example 1 of the present application;
FIG. 2 is the infrared test results of the surfactant of example 1 of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the following describes in detail various embodiments of the present application with reference to the embodiments. However, those of ordinary skill in the art will understand that in various embodiments of the present application, numerous technical details have been set forth in order to provide a better understanding of the present application. However, the claimed application may be practiced without these specific details and with various changes and modifications based on the following embodiments.
The main chemical components of the limestone used in the examples of the present application are shown in Table 1:
TABLE 1 Main chemical Components of limestone (wt%)
| Composition of the components | CaO | MgO | SiO 2 | Fe 2 O 3 | Al 2 O 3 |
| Content of | 50.03 | 0.71 | 9.1 | 0.60 | 1.18 |
Example 1:
the desulfurization and upgrading transformation method of the garbage incineration system comprises the following steps of:
firstly, adding a high-temperature desulfurizing agent into a high-temperature section of an incinerator at a temperature above 850 ℃, wherein the conveying mode is wind power conveying. The process carries out primary desulfurization on the basic value in the furnace through the synergistic effect of the desulfurization main component in the medicament and the catalyst; then the steam after the flue gas is subjected to heat exchange by the waste heat boiler is used for generating electricity by a steam turbine; the flue gas firstly enters a desulfurization reaction tower to carry out semi-dry desulfurization, and the process can improve the concentration of lime slurry by adding a solubilizer in the lime slurry preparation process (namely a lime slurry preparation system), so that the concentration of lime slurry is ensured to be improved on the premise of not changing the fluidity of lime slurry; after the semi-dry method secondary desulfurization, the flue gas enters a cloth bag dust remover and other systems for dust removal, and is discharged out of an incineration system through a chimney to enter the atmosphere.
It should be noted that:
in the high temperature section: adding a combined desulfurizing agent in a temperature range of 850-1050 ℃, and spraying the combined desulfurizing agent to a high-temperature section of a garbage incinerator in a manner of providing pneumatic conveying through a Roots blower and the like, wherein the adding amount is 4kg/t of garbage;
in the desulfurization reaction tower part: a solubilizer is required to be added into the lime slurry preparation tank body, so that the concentration of the lime slurry is improved; namely, the preparation of lime slurry comprises the following steps:
adding deionized water (solid-to-liquid ratio is 4mg:1 mL) into limestone, uniformly mixing, adding a solubilizer (adding amount is 500mg/L lime slurry), and uniformly stirring to obtain lime slurry; the solubilizer comprises citric acid and surfactant; the molar ratio of the two is 1:0.2.
Preparation of a surfactant:
and adding tetramethyl propylene diamine (the molar ratio of the 5-bromopentanal glycol acetal to the ethanol is 2.2:1), adding ethanol (the dosage ratio of the 5-bromopentanal glycol acetal to the ethanol is 0.25g:1 mL), carrying out reflux reaction for 48h at 80 ℃, then carrying out rotary evaporation, adding acetone at 0 ℃, extracting, washing the extract with the acetone, and drying to obtain the surfactant.
Preparation of modified calcium hydroxide:
and (3) adding surfactant (the mass ratio of the surfactant to the calcium hydroxide is 0.065:1) and a proper amount of water into the calcium hydroxide which is sieved by a 200-mesh sieve, mechanically stirring and heating the mixture to be pasty, and then drying and grinding the mixture into powder at 120 ℃ to obtain the modified calcium hydroxide.
Preparation of a combined desulfurizing agent:
mixing zinc acetate, cerous nitrate and zirconyl nitrate (the molar ratio of the zinc acetate to the cerous nitrate is 1:3:0.9), adding distilled water, glycol and acetone (the volume ratio of the zinc acetate to the mixed solvent is 1:2:1) into the mixed solvent (the dosage ratio of the zinc acetate to the mixed solvent is 0.08 mol:1L), dissolving the mixed solvent, continuously stirring the mixed solvent at a high speed for 1h, adding urea (the molar ratio of the mixture of the zinc acetate, the cerous nitrate and the zirconyl nitrate is 0.05:1), ultrasonically mixing the mixed solvent for 15min, then adding a surfactant (the molar ratio of the mixed solvent to the urea is 1.6:1), continuously ultrasonically stirring the mixed solvent for 25min, placing the mixed solvent into a high-pressure reaction kettle, sealing the mixed solvent, controlling the pressure to be 2MPa, keeping the temperature at 240 ℃ for 13h, cooling the mixed solvent, taking the mixed solvent out, filtering the mixed solvent, and drying the mixed solvent to obtain a composite metal oxide;
adding modified calcium hydroxide and attapulgite into a composite metal oxide (the mass ratio of the three is 1:5:0.8), adding water (the water is used in an amount which can be used for uniformly mixing the composite metal oxide and the attapulgite), uniformly mixing, kneading, forming, granulating, drying at 110 ℃ for 10 hours, and roasting at 500 ℃ for 2 hours to obtain the combined desulfurizing agent with the average particle diameter of 4.2mm.
Example 2:
the desulfurization and standard-raising transformation method of the garbage incineration system is different from that of the embodiment 1: the combined desulfurizing agent was prepared in this example; lime slurry was prepared in this example.
The preparation of the combined desulfurizing agent differs from example 1 in that:
the molar ratio of zinc acetate to cerium nitrate to zirconyl nitrate is 1:2.4:0.6; distilled water, glycol and acetone in the volume ratio of 1:1.6:0.8; the dosage ratio of the zinc acetate to the mixed solvent is 0.05mol:1L; the molar ratio of urea to the zinc acetate, cerous nitrate and zirconyl nitrate mixture is 0.03:1; the molar ratio of the surfactant to the urea is 1.3:1; the mass ratio of the composite metal oxide to the modified calcium hydroxide (prepared in the embodiment) to the attapulgite is 1:4.2:0.7; the average particle size of the combined desulfurizing agent is 3.7mm.
The preparation of the surfactant was the same as in example 1.
The modified calcium hydroxide was prepared differently from example 1: the mass ratio of the surfactant to the calcium hydroxide is 0.055:1.
Lime slurry was prepared as opposed to example 1:
the solid-to-liquid ratio of the limestone to the deionized water is 3.2mg to 1mL; the addition amount of the solubilizer is 420mg/L lime slurry.
The solubilizer comprises benzoic acid and a surfactant; the molar ratio of the two is 1:0.12.
Example 3:
the desulfurization and standard-raising transformation method of the garbage incineration system is different from that of the embodiment 1: the combined desulfurizing agent was prepared in this example; lime slurry was prepared in this example.
The preparation of the combined desulfurizing agent differs from example 1 in that:
the molar ratio of zinc acetate to cerium nitrate to zirconyl nitrate is 1:3.8:1.4; distilled water, glycol and acetone in the volume ratio of 1:2.4:1.1; the dosage ratio of the zinc acetate to the mixed solvent is 0.11mol:1L; the molar ratio of urea to the zinc acetate, cerous nitrate and zirconyl nitrate mixture is 0.07:1; the molar ratio of the surfactant to the urea is 1.9:1; the mass ratio of the composite metal oxide to the modified calcium hydroxide (prepared in the embodiment) to the attapulgite is 1:5.8:0.9; the average particle size of the combined desulfurizing agent is 5.1mm.
The preparation of the surfactant was the same as in example 1.
The modified calcium hydroxide was prepared differently from example 1: the mass ratio of the surfactant to the calcium hydroxide is 0.075:1.
Lime slurry was prepared as opposed to example 1:
the solid-to-liquid ratio of limestone to deionized water was 4.8mg to 1mL; the amount of solubilizer added was 580mg/L lime slurry.
The solubilizer comprises adipic acid and a surfactant; the molar ratio of the two is 1:0.28.
Example 4:
the desulfurization and standard-raising transformation method of the garbage incineration system is different from that of the embodiment 1: the combined desulfurizing agent was prepared in this example; lime slurry was prepared in this example.
The preparation of the combined desulfurizing agent differs from example 1 in that:
the molar ratio of zinc acetate to cerium nitrate to zirconyl nitrate is 1:2.7:0.7; distilled water, glycol and acetone in the volume ratio of 1:1.8:0.95; the dosage ratio of zinc acetate to the mixed solvent is 0.095mol:1L; the molar ratio of urea to the zinc acetate, cerous nitrate and zirconyl nitrate mixture is 0.055:1; the molar ratio of the surfactant to the urea is 1.7:1; the mass ratio of the composite metal oxide to the modified calcium hydroxide (prepared in the embodiment) to the attapulgite is 1:4.9:0.85; the average particle size of the combined desulfurizing agent is 4.5mm.
The preparation of the surfactant was the same as in example 1.
The modified calcium hydroxide was prepared differently from example 1: the mass ratio of the surfactant to the calcium hydroxide is 0.068:1.
Lime slurry was prepared as opposed to example 1:
the solid-to-liquid ratio of limestone to deionized water was 4.4mg to 1mL; the addition amount of the solubilizer is 485mg/L lime slurry.
The solubilizer comprises succinic acid and a surfactant; the molar ratio of the two is 1:0.23.
Example 5:
the desulfurization and standard-raising transformation method of the garbage incineration system is different from that of the embodiment 1: lime slurry was prepared in this example.
Lime slurry was prepared as opposed to example 1: in the solubilizer, an equimolar amount of the citric acid derivative is used instead of the organic acid.
Preparation of citric acid derivatives:
mixing citric acid and hydroxyethylidene diphosphonic acid (the molar ratio of the two is 1:3.3), adding benzenesulfonic acid (the addition amount is 0.51wt% of citric acid) and toluene (the solid-liquid ratio of citric acid to toluene is 0.5g:1 mL), then dropwise adding phosphoric acid (the addition amount ratio of citric acid is 1 drop: 2.5 g), heating and refluxing, carrying out water diversion through a water diversion device, carrying out reduced pressure distillation after reacting for 7 hours, cooling to room temperature, dropwise adding saturated sodium bicarbonate solution until the pH value of the system is neutral, extracting by adopting anhydrous diethyl ether, washing for 5 times by using saturated saline water, drying by using anhydrous sodium sulfate, and collecting fractions at 162-163 ℃ through reduced pressure distillation to obtain citric acid derivatives, wherein the chemical structure is shown as formula I:
I
1 H NMR（400 MHz，D 2 O）：δ：2.75（s，4H，-CH 2 ），1.69（s，9H，-CH 3 ）。
example 6:
the desulfurization and standard-raising transformation method of the garbage incineration system is different from that of the embodiment 1: lime slurry was prepared in this example.
Lime slurry was prepared as opposed to example 1: in the solubilizer, an equimolar amount of the citric acid derivative is used instead of the organic acid.
The preparation of the citric acid derivative differs from example 5 in that: the equal molar weight of 4-hydroxyethyl piperazine ethane sulfonic acid is adopted to replace hydroxy ethylidene diphosphonic acid, and the chemical structure is shown as a formula II:
II
1 H NMR（400 MHz，D 2 O）：δ：4.37（t，6H，-CH 2 ），3.11、2.99、2.82、2.27（42H，-CH 2 ），2.73（s，4H，-CH 2 ）。
example 7:
the desulfurization and upgrading modification method of the garbage incineration system is different from that of the embodiment 5: lime slurry was prepared in this example.
Lime slurry was prepared differently from example 5: in the solubilizer, the surfactant is tetradecyl trimethyl ammonium bromide.
The preparation of the citric acid derivative was the same as in example 5.
Example 8:
the desulfurization and upgrading modification method of the garbage incineration system is different from that of the embodiment 6: lime slurry was prepared in this example.
Lime slurry was prepared in a manner different from example 6: in the solubilizer, the surfactant is tetradecyl trimethyl ammonium bromide.
The preparation of the citric acid derivative was the same as in example 6.
Example 9:
the desulfurization and upgrading modification method of the garbage incineration system is different from that of the embodiment 5: lime slurry was prepared in this example.
Lime slurry was prepared differently from example 5: in the solubilizer, the organic acid is a mixture of citric acid derivatives prepared in example 5 and example 6, and the molar ratio of the two is 1:1.
Example 10:
the desulfurization and standard-raising transformation method of the garbage incineration system is different from that of the embodiment 1: the combined desulfurization agent was prepared in this example and the lime slurry was prepared in this example.
The preparation of the combined desulfurizing agent differs from example 1 in that:
the surfactant is tetradecyl trimethyl ammonium bromide; modified calcium hydroxide was prepared in this example.
The modified calcium hydroxide was prepared differently from example 1: the surfactant is tetradecyl trimethyl ammonium bromide.
Lime slurry was prepared as opposed to example 1: in the solubilizer, the surfactant is tetradecyl trimethyl ammonium bromide.
Test example 1:
infrared sign
The testing is carried out by adopting a Fourier infrared spectrometer, and the testing range is 500-4000 cm by adopting a potassium bromide tabletting method -1 。
The surfactant prepared in example 1 was subjected to the above test, and the results are shown in fig. 2. From the analysis of the graph, the graph shows that the distance between 2800 cm and 3000cm -1 An infrared characteristic absorption peak of 1125cm appears near the methylene group -1 An infrared characteristic absorption peak with ether bond near 930cm -1 Infrared characteristic absorption of nearby epoxy groupsPeak harvest indicates successful surfactant preparation in example 1.
Test example 2:
sulfur capacity performance determination of combined desulfurizing agent
The test method is performed with reference to the standard specified by HG/T2513.
The above tests were carried out on the combined desulfurizing agents prepared in examples 1 to 4 and example 10, and the results are shown in table 2:
TABLE 2 Sulfur capacity Performance test results
| Sample of | Sulfur capacity (g/kg:%) |
| Example 1 | 60.3 |
| Example 2 | 60.0 |
| Example 3 | 60.8 |
| Example 4 | 60.2 |
| Example 10 | 45.7 |
From the data analysis in Table 2, the sulfur capacity of the combined desulfurizing agent prepared in example 1 is obviously higher than that of example 10, which shows that the use of 5-bromopentanal glycol acetal to prepare the surfactant and the compounding of other components to prepare the combined desulfurizing agent can obviously enhance the desulfurizing activity of the combined desulfurizing agent, the sulfur capacity is obviously improved, and the desulfurizing efficiency is effectively increased.
Test example 3:
limestone solubility determination
The limestone solubility test method was performed with reference to the standard titration method specified in DL/T943.
The lime slurries prepared in examples 7-10 were tested as described above and the results are shown in table 3:
TABLE 3 solubility test results
| Sample of | Dissolution fraction (%) |
| Example 7 | 86.7 |
| Example 8 | 85.1 |
| Example 9 | 92.8 |
| Example 10 | 79.4 |
From the data analysis in table 3, the dissolution fraction of the lime slurry prepared in example 7 and example 8 is significantly better than that of example 10, and the effect of example 9 is significantly better than that of examples 7-8, which shows that the citric acid derivative prepared by mixing and reacting hydroxyethylidene diphosphonic acid or 4-hydroxyethylpiperazine ethanesulfonic acid with citric acid is used as an organic acid in the solubilizer, so that the solubility of limestone can be significantly increased; and under the condition that the modified substance of the hydroxyethylidene diphosphonic acid and the modified substance of the 4-hydroxyethylpiperazine ethanesulfonic acid are modified together, the enhancement effect on the solubility of the limestone is better.
SO 2 Determination of absorption Rate
The test system is a double-stirring reaction kettle with a horizontal gas-liquid interface, the reaction kettle is composed of organic glass, and the inner diameter of the reaction kettle is 100mm and the height of the reaction kettle is 160mm. In the experimental process, the gas phase stirring speed is 250r/min, the liquid phase stirring speed is 120r/min, the volume of lime slurry in the kettle is 800mL, the gas flow rate is 500mL/min, and the experimental absorption time is 30min. SO was calculated according to the following formula 2 Absorption rate:
SO 2 absorption rate=vp/(RTS) (Y 1 -Y 2 )
Wherein V represents the flow rate of the mixed gas, m 3 S; p represents the operating pressure, pa; r represents a gas constant, 9.314 J.mol -1 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the T represents the reaction temperature, K; s represents the area of gas-liquid phase boundary, m 2 ；Y 1 Representing the reactor inlet SO 2 A volume fraction; y is Y 2 Representing the reactor outlet SO 2 Volume fraction.
The lime slurries prepared in examples 7-10 were tested as described above and the results are shown in table 4:
table 4 SO 2 Absorption Performance test results
| Sample of | SO 2 Absorption Rate (. Times.10) -5 mol/(m 2 ·s)） |
| Example 7 | 9.33 |
| Example 8 | 9.25 |
| Example 9 | 10.18 |
| Example 10 | 8.43 |
From the analysis of the data in Table 4, it is seen that the SO's of the lime slurries prepared in example 7 and example 8 2 The absorption rate is obviously higher than that of example 10, and the effect of example 9 is obviously better than that of examples 7-8, which shows that the citric acid derivative prepared by mixing and reacting the hydroxyethylidene diphosphonic acid or 4-hydroxyethylpiperazine ethanesulfonic acid with citric acid can be used as organic acid in solubilizer, and can obviously enhance the SO of lime slurry 2 Is a natural absorption function; and in the case of co-modification of hydroxyethylidene diphosphonic acid modification and 4-hydroxyethylpiperazine ethanesulfonic acid modification, the lime slurry SO 2 The enhancement effect of the absorption effect is better.
Test example 4:
analysis of treatment results of the desulfurization and upgrading modification methods of the garbage incineration systems in examples 1-10 are shown in table 5:
TABLE 5 analysis of results
| Sample of | SO 2 Emission concentration decrease rate (%) | NO x Overall emission concentration drop rate (%) |
| Example 1 | 40.6 | 33.2 |
| Example 2 | 41.0 | 32.9 |
| Example 3 | 40.7 | 33.1 |
| Example 4 | 40.9 | 33.4 |
| Example 5 | 47.1 | 36.8 |
| Example 6 | 46.2 | 35.3 |
| Example 7 | 38.0 | 33.5 |
| Example 8 | 37.1 | 32.0 |
| Example 9 | 43.4 | 38.7 |
| Example 10 | 32.8 | 30.0 |
As can be seen from the data analysis in Table 5, the SO after treatment by the method provided in example 1 2 Emission concentration decrease rate and NO x The overall emission concentration drop rate is obviously higher than that of example 10, which shows that the surfactant prepared by adopting the 5-bromopentanal glycol acetal is compounded with other components to prepare the combined desulfurizing agent, and the combined desulfurizing agent is compounded with other components, so that the treatment effect, sulfur dioxide and NO of the treatment method can be effectively improved x The overall emission concentration is significantly reduced. The effects of example 5 and example 6 are significantly better than those of example 1, the effects of example 7 and example 8 are significantly better than those of example 10, and the effects of example 9 are significantly better than those of examples 7-8, indicating that the citric acid derivative prepared by mixing and reacting hydroxyethylidene diphosphonic acid or 4-hydroxyethylpiperazine ethanesulfonic acid with citric acid is used as an organic acid in a solubilizer and in a desulfurization treatment of a garbage incineration system, and can further enhance the desulfurization treatment effect, sulfur dioxide and NO x The overall emission concentration is further reduced; and under the condition that the modified hydroxyethylidene diphosphonic acid and the modified 4-hydroxyethylpiperazine ethanesulfonic acid are modified together, the enhancement effect on the desulfurization treatment effect is better.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The foregoing is merely illustrative of the present application, and the present application is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (5)
1. A combined desulfurizing agent comprises a calcium-based composite metal oxide with a catalytic reaction function, wherein the calcium-based composite metal oxide is granular, and the grain diameter is 3-6 mm;
the composite metal oxide includes zinc oxide, zirconium oxide and cerium oxide;
the preparation method of the combined desulfurizing agent comprises the following steps:
mixing zinc acetate, cerous nitrate and zirconyl nitrate, adding distilled water, glycol and acetone mixed solvent for dissolution, adding urea and surfactant, controlling the pressure to be 1.5-2.5 MPa, preserving heat for 10-15 h at 220-250 ℃, filtering and drying to obtain a composite metal oxide;
adding modified calcium hydroxide and attapulgite into the composite metal oxide, adding water, uniformly mixing, kneading, forming, drying, and roasting at 400-600 ℃ for 1-3 hours to obtain a combined desulfurizing agent;
the preparation method of the modified calcium hydroxide comprises the following steps:
taking screened calcium hydroxide, adding a surfactant and a proper amount of water, mechanically stirring and heating to paste, and then drying and grinding into powder at 120-125 ℃ to obtain modified calcium hydroxide;
the surfactant comprises quaternary ammonium salt surfactant; the quaternary ammonium salt surfactant comprises a product of a chemical reaction of 5-bromopentanal glycol acetal and tetramethyl propylene diamine.
2. The combined desulfurizing agent according to claim 1, wherein the molar ratio of zinc acetate, cerium nitrate and zirconyl nitrate is 1:2-4:0.5-1.5.
3. The combined desulfurizing agent according to claim 1, wherein the mass ratio of the composite metal oxide, the modified calcium hydroxide and the attapulgite is 1:4-6:0.6-1.
4. A method for desulfurizing and upgrading a garbage incineration system, comprising the following steps: casting the combined desulfurizing agent according to claim 1 in a high temperature section of a garbage incineration system; meanwhile, in the desulfurization reaction tower part, adding a solubilizing agent comprising organic acid into the lime slurry preparation tank body; the organic acid comprises citric acid, citric acid derivatives, benzoic acid, adipic acid or succinic acid; the citric acid derivative comprises a product of hydroxyethylidene diphosphonic acid esterification modified citric acid and/or a product of 4-hydroxyethylpiperazine ethanesulfonic acid esterification modified citric acid.
5. The method for improving desulfurization standard of a garbage incineration system according to claim 4, which is characterized in that the addition amount of the combined desulfurizing agent is 3-6 kg/t garbage.
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| CN117046865B (en) * | 2023-10-11 | 2024-01-23 | 杭州尚善若水环保科技有限公司 | Method for preparing in-furnace desulfurization and denitrification medicament by utilizing waste incineration fly ash |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4836993A (en) * | 1983-09-27 | 1989-06-06 | Amoco Corporation | Process for removing sulfur oxides from a gas |
| CN103657342A (en) * | 2013-12-10 | 2014-03-26 | 陕西省石油化工研究设计院 | High-efficiency regenerative SO2 absorbent |
| CN103736357A (en) * | 2013-12-12 | 2014-04-23 | 芜湖中路实业有限责任公司 | Pottery clay desulfurizer and preparation method thereof |
| CN103933836A (en) * | 2008-03-07 | 2014-07-23 | 太平洋水泥株式会社 | System and method for treating bleed gas from cement kiln |
| CN105384262A (en) * | 2015-10-29 | 2016-03-09 | 华电电力科学研究院 | Special scale inhibitor for wet desulfurization system |
| CN105854917A (en) * | 2015-01-22 | 2016-08-17 | 中国石油化工股份有限公司 | Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method |
| CA2969445A1 (en) * | 2016-06-07 | 2017-12-07 | China Petroleum & Chemical Corporation | Catalyst, preparing method and use thereof, and sulfur recovering method |
| CN109370646A (en) * | 2018-11-13 | 2019-02-22 | 陈开龙 | Catalytically cracked gasoline desulfurization method for modifying |
| CN111073717A (en) * | 2019-12-30 | 2020-04-28 | 李晓澎 | Natural gas purifying agent and method for purifying natural gas |
| CN111359601A (en) * | 2020-04-07 | 2020-07-03 | 中海油天津化工研究设计院有限公司 | Catalyst for improving desulfurization performance of calcium hydroxide |
| CN112742362A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Coke-oven gas hydrodesulfurization catalyst and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7132093B2 (en) * | 2002-06-05 | 2006-11-07 | UNIVERSITé LAVAL | Mesoporous mixed oxide materials as a new class of SO2 resistant catalysts for hydrocarbon oxidation |
-
2023
- 2023-08-08 CN CN202310990619.0A patent/CN116688745B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4836993A (en) * | 1983-09-27 | 1989-06-06 | Amoco Corporation | Process for removing sulfur oxides from a gas |
| CN103933836A (en) * | 2008-03-07 | 2014-07-23 | 太平洋水泥株式会社 | System and method for treating bleed gas from cement kiln |
| CN103657342A (en) * | 2013-12-10 | 2014-03-26 | 陕西省石油化工研究设计院 | High-efficiency regenerative SO2 absorbent |
| CN103736357A (en) * | 2013-12-12 | 2014-04-23 | 芜湖中路实业有限责任公司 | Pottery clay desulfurizer and preparation method thereof |
| CN105854917A (en) * | 2015-01-22 | 2016-08-17 | 中国石油化工股份有限公司 | Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method |
| CN105384262A (en) * | 2015-10-29 | 2016-03-09 | 华电电力科学研究院 | Special scale inhibitor for wet desulfurization system |
| CA2969445A1 (en) * | 2016-06-07 | 2017-12-07 | China Petroleum & Chemical Corporation | Catalyst, preparing method and use thereof, and sulfur recovering method |
| CN109370646A (en) * | 2018-11-13 | 2019-02-22 | 陈开龙 | Catalytically cracked gasoline desulfurization method for modifying |
| CN112742362A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Coke-oven gas hydrodesulfurization catalyst and preparation method and application thereof |
| CN111073717A (en) * | 2019-12-30 | 2020-04-28 | 李晓澎 | Natural gas purifying agent and method for purifying natural gas |
| CN111359601A (en) * | 2020-04-07 | 2020-07-03 | 中海油天津化工研究设计院有限公司 | Catalyst for improving desulfurization performance of calcium hydroxide |
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