CN111847717A - Method for cooperatively treating organic hazardous waste liquid by using cement kiln - Google Patents
Method for cooperatively treating organic hazardous waste liquid by using cement kiln Download PDFInfo
- Publication number
- CN111847717A CN111847717A CN202010709077.1A CN202010709077A CN111847717A CN 111847717 A CN111847717 A CN 111847717A CN 202010709077 A CN202010709077 A CN 202010709077A CN 111847717 A CN111847717 A CN 111847717A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- kiln
- hazardous waste
- clinker
- heavy metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 102
- 239000004568 cement Substances 0.000 title claims abstract description 64
- 239000002920 hazardous waste Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 80
- 239000003245 coal Substances 0.000 claims abstract description 70
- 239000000446 fuel Substances 0.000 claims abstract description 55
- 238000002485 combustion reaction Methods 0.000 claims abstract description 43
- 238000002347 injection Methods 0.000 claims abstract description 24
- 239000007924 injection Substances 0.000 claims abstract description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 230000002195 synergetic effect Effects 0.000 claims abstract description 10
- 208000005156 Dehydration Diseases 0.000 claims abstract description 9
- 230000018044 dehydration Effects 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 9
- 238000001784 detoxification Methods 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 150000002500 ions Chemical class 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000012024 dehydrating agents Substances 0.000 claims description 21
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 239000012716 precipitator Substances 0.000 claims description 18
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical group OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 10
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 10
- 229940068041 phytic acid Drugs 0.000 claims description 10
- 235000002949 phytic acid Nutrition 0.000 claims description 10
- 239000000467 phytic acid Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000004155 Chlorine dioxide Substances 0.000 claims description 7
- 235000012255 calcium oxide Nutrition 0.000 claims description 7
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002480 mineral oil Substances 0.000 claims description 7
- 235000010446 mineral oil Nutrition 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 229940037003 alum Drugs 0.000 claims description 2
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 16
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 2
- 150000008282 halocarbons Chemical class 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000000779 smoke Substances 0.000 description 21
- 239000002910 solid waste Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000002817 coal dust Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 231100000419 toxicity Toxicity 0.000 description 7
- 230000001988 toxicity Effects 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000010808 liquid waste Substances 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical group [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 229910052785 arsenic Inorganic materials 0.000 description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 231100000252 nontoxic Toxicity 0.000 description 5
- 230000003000 nontoxic effect Effects 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 239000010849 combustible waste Substances 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000004069 differentiation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical group [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000003473 refuse derived fuel Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000010887 waste solvent Substances 0.000 description 2
- 206010049040 Weight fluctuation Diseases 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- -1 alcohol amine Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- INFDPOAKFNIJBF-UHFFFAOYSA-N paraquat Chemical compound C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 INFDPOAKFNIJBF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002893 slag Substances 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
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/46—Solid fuels essentially based on materials of non-mineral origin on sewage, house, or town refuse
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
- F27B7/34—Arrangements of heating devices
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D99/00—Subject matter not provided for in other groups of this subclass
- F27D99/0001—Heating elements or systems
- F27D99/0003—Heating elements or systems with particulate fuel, e.g. aspects relating to the feeding
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D99/00—Subject matter not provided for in other groups of this subclass
- F27D99/0001—Heating elements or systems
- F27D99/0005—Injecting liquid fuel
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/542—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/125—Fuels from renewable energy sources, e.g. waste or biomass
Abstract
A method for cooperatively treating organic hazardous waste liquid by a cement kiln comprises the following steps: (1) detoxification treatment; (2) carrying out dehydration treatment; (3) and (5) performing synergistic treatment on the cement kiln. The method has the advantages of simple process and less investment, can effectively eliminate the strong biotoxicity of the hazardous waste liquid, can efficiently enrich and remove heavy metals and/or remove halogen in halogenated hydrocarbon, obtains high-heat-value liquid fuel with good combustion performance, and has no secondary pollution; the invention can effectively obtain hydrocarbon energy in the hazardous waste liquid, directly increase the flame temperature of the coal-injection pipe burner, accelerate the oxidation combustion of the coal powder, increase the timely burnout rate of the coal powder, and improve the kiln condition and the sintering quality of clinker. The method is beneficial to clean resource utilization of the hazardous waste liquid containing hydrocarbon, promotes clean combustion of the coal powder entering the kiln, can effectively save fire coal, is beneficial to environmental protection, and is beneficial to the sustainable development of green, low-carbon and circular economy.
Description
Technical Field
The invention relates to a recycling method of organic hazardous waste liquid, in particular to a method for cooperatively treating the organic hazardous waste liquid by a cement kiln.
Background
The hazardous waste in China has the characteristics of large production amount, multiple types and wide sources, and is divided into 46 types in the national hazardous waste list (2016 edition), and 479 types are counted. In more than 20 years, China has established a relatively complete hazardous waste management system, and relatively complete hazardous waste disposal facilities are established nationwide, and three major disposal technologies mainly including incineration disposal technology, solidification stabilization technology and cement kiln co-disposal are formed. At present, the cement kiln is used for disposing hazardous wastes together, which is one of the most important and effective technical approaches.
The cement kiln co-disposal of hazardous wastes in foreign developed countries starts in the 70 th century, and is rapidly developed and generally applied, for example, in 1972, the cement kiln co-disposal of hazardous wastes is started in the U.S., most cement plants have reported that one or more wastes are used as alternative fuels, and at present, the utilization rate of the alternative fuels of most cement plants in the U.S. reaches 20-70%. Research on the preparation of alternative fuels by using combustible wastes from the last 70 th century in developed countries such as Germany, Switzerland, France, Austria and Belgium in Europe is carried out, and taking a Lixhe cement factory in Heideberg in Belgium as an example, the added alternative fuels sprayed into a main burner position of a kiln head comprise inflammable high-heat-value wastes such as sawdust, animal feeds, waste solvents, waste oil and plastics after adsorbing the wastes; the alternative fuel which is put into the pre-decomposition furnace from the top of the pre-decomposition furnace comprises fine-grained or powdery sawdust, filter soil, plastics, RDF (refuse derived Fuel), polluted soil, dried organic sludge, papermaking sludge, animal feed, seeds and the like which adsorb the waste, and the fuel substitution rate reaches 65-90%.
In the last decade, the policy documents issued by the ministry of China in succession locate the cement kiln to co-dispose waste at the strategic height of promoting environmental protection, developing circular economy, promoting energy conservation and emission reduction, and adjusting industrial structure. The progress of the waste co-treatment of the cement kiln in China is effectively promoted, and nearly two hundred cement enterprises which co-treat dangerous waste or pass the environmental evaluation or are in the environmental evaluation stage are developed. However, compared with the developed countries abroad, in the aspect of preparing the alternative fuel, the cement enterprises in China are influenced by the investment and cost bearing capacity due to the huge difference of the national conditions and the exchange rate converted cement price, and the waste alternative fuel has the practical problems of insufficient stable components, nonuniform shape, low heat value and the like, so that the alternative fuel product is insufficiently combusted in the cement kiln, and the energy consumption of the system is increased. In the aspect of replacing fuel, the average replacement rate of the fuel is far lower than that of developed countries in China in the cement production process by more than 30%, the maximum replacement rate is more than 90%, the replacement rate of fuel wastes of most cement enterprises in China is 0%, and the replacement rate of the most advanced typical enterprise fuel wastes is less than 10%.
Although cement kiln systems and clinker minerals have great compatibility, wastes easily cause adverse effects on the working condition stability of the kiln systems, pollutant discharge and cement clinker performance, technical workers at home and abroad carry out a great deal of research and practice for solving or reducing the effects of various wastes including hazardous wastes on the cement kiln systems in the cooperative treatment of the cement kiln systems, and the conventional cooperative treatment method can be roughly divided into the following steps:
(1) The method for burning kiln head sprayed into rotary kiln mainly includes three modes:
(A) after the hazardous waste liquid (water-containing waste liquid, waste solvent waste liquid and the like) is subjected to blending, filtering and pretreatment, the hazardous waste liquid is pumped to a kiln hood and sprayed into a rotary kiln for incineration. The method is suitable for the cooperative treatment of the hazardous waste liquid with high calorific value, low chlor-alkali and low moisture, is equivalent to oil injection combustion, and can save a large amount of fuel, but the hazardous waste liquid with high water content or high chlor-alkali element content can influence the burning of the head coal, or generate a large amount of chloric acid mist and the like to influence the kiln condition and increase the energy consumption.
(B) The powdery hazardous waste is conveyed to a kiln head cover through pipeline compressed air and is sprayed into the rotary kiln for incineration. The method has the advantages that firstly, the method influences the burning of the head coal and increases the heat consumption, secondly, the method is not suitable for dangerous wastes containing easily reduced and volatilized heavy metals such as mercury and the like and high in chlor-alkali content, the kiln condition is influenced, and the applicable treatment capacity is generally very small.
(C) Combustible high-heat-value wastes such as powdery or fine granular anhydrated sawdust, animal feed, plastics and the like are conveyed to a kiln hood by a pipeline and sprayed into a rotary kiln for incineration. The method can save a large amount of fuel, but has high drying and crushing treatment cost.
(2) The method for pushing the kiln head/kiln tail into the rotary kiln for burning mainly comprises the steps of pushing large combustible waste such as rubber tires, and has high requirements on a feeding and pushing mechanism.
(3) The method for burning the combustible waste in the grate cooler in the kiln head cover is characterized in that the combustible waste is directly put into the grate cooler to burn, so that the cooling quality of clinker is easily influenced, the oxygen-containing concentration of secondary air entering a kiln and tertiary air entering the kiln is reduced, and the pulverized coal burning and the kiln condition of the kiln are influenced. The method is only suitable for heat-absorbing materials or low-heat-value materials and materials which need targeted pretreatment on contained heavy metals, chlor-alkali sulfur and the like.
(4) The method for co-processing the waste gas fed into the kiln tail smoke chamber comprises the following three modes: (A) and directly sending the crushed solid waste into a kiln tail smoke chamber for cooperative treatment. (B) Directly pumping the slurry material into a kiln tail smoke chamber for cooperative treatment. (C) The powdery material is directly sprayed into a kiln tail smoke chamber by pipeline compressed air for cooperative treatment. A common drawback of this type of process is: firstly, easily cause the material accumulation of kiln tail smoke chamber to glue stifled. And secondly, heavy metals in the solid waste are not subjected to reduction inhibition and pre-curing treatment, so that reduction volatilization of the heavy metals and volatilization of chlor-alkali sulfur are easily caused, the skinning of a smoke chamber, a throat and the like is aggravated, the stability of kiln conditions is influenced, and the heat consumption is increased. Because the kiln tail smoke chamber is an anoxic channel for communicating the rotary kiln with the upper decomposing furnace, the head coal which is not burnt out in time is accelerated to fly to the smoke chamber along with wind, and a small amount of coal dust particles also fall along with materials along with wind and star fire at the cone part of the upper decomposing furnace, so that the smoke chamber is always in a weak reducing atmosphere or a strong reducing atmosphere state. Thirdly, the combustible substances such as carbon-containing organic matters, sulfides and the like in the solid waste are not subjected to transitional reduction inhibition treatment, wherein the combustible substances can aggravate the reduction skinning of a smoke chamber and a throat.
(5) Sending the raw materials into a predecomposition furnace for a synergistic treatment method, which mainly comprises the following steps:
(A) and directly feeding the crushed carbon-containing organic solid waste serving as alternative fuel into the decomposing furnace from the inlet position of a tertiary air pipe of the decomposing furnace for cooperative treatment. The synergistic disposal mode is expected to preferentially heat and burn the solid waste by the high-temperature oxygen-containing tertiary air, but because the combustion performance of the carbon-containing organic solid waste is much poorer than that of fire coal, most of the carbon-containing organic solid waste contains a lot of adsorbed water and crystal water, the cold solid waste entering the decomposing furnace has poorer combustion performance, customers visually influence the combustion of pulverized coal in the decomposing furnace, most of the carbon-containing organic solid waste increase coal consumption, influence the working condition of a kiln system and increase the emission of heavy metals and pollutants in waste gas.
(B) The slurry hazardous waste or solid/plastic hazardous waste is smashed into slurry slag hazardous waste, and then oil substances are added and mixed, and the mixture is pumped into a decomposing furnace from a tertiary air pipe inlet position of the decomposing furnace as a substitute fuel for cooperative treatment. Although oil is added for supporting combustion and is added at an ideal position of a high-temperature oxygen-containing tertiary air port, the combustion performance of the carbon-containing organic matter solid waste is much lower than that of coal, most of the carbon-containing organic matter solid waste contains a lot of adsorbed water, combined water and free water, and the actual operation condition mostly influences the combustion of coal powder in a decomposing furnace, but increases the coal consumption, influences the working condition of a kiln system and increases the emission of heavy metals and pollutants in waste gas.
(C) The pretreated and dried combustible material is used as a substitute fuel and is put into the pre-decomposition furnace from the upper part (or the top) of the pre-decomposition furnace for cooperative treatment, and the pretreated and dried substitute fuel is generally combustible granular or powdery sawdust, filter soil, plastics, RDF, polluted soil, dried organic sludge, paper making sludge and the like which adsorb waste. The method can replace a large amount of tail coal, but the pretreatment and drying costs are high, most cement enterprises in China cannot bear the cost exceeding that of coal burning, and the secondary pollution problem in most pretreatment processes which is more troublesome is difficult to solve or extremely high in cost.
(6) The method is suitable for treating common solid waste to replace raw materials, and the dangerous waste which is not subjected to targeted effective pretreatment may have the hidden trouble of pollution diffusion of heavy metal/toxic harmful substances.
Obviously, the existing technology of using carbon-containing organic hazardous wastes as alternative fuels has the defects, particularly, the heavy-metal-containing hydrocarbon hazardous waste liquid is only required to be directly sprayed into a kiln from the kiln head for incineration, and the danger is not clear! Heavy metals, particularly heavy metals which are easy to reduce and volatilize, are caused to migrate with hot wind into dust of the humidifying tower and diffuse in the atmosphere; the high-water-content hydrocarbon dangerous waste liquid is directly sprayed into the kiln for incineration, a large amount of heat is firstly absorbed for vaporization of a large amount of water to influence the timely burnout rate of head coal, the combustion of tail coal in the decomposing furnace is also directly influenced by high-concentration steam, the probability of powder arching, sticking and blocking of a preheater system is increased, and the clinker coal consumption is increased.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide a method for cooperatively treating organic hazardous waste liquid by using a cement kiln, which can efficiently utilize hydrocarbon in the organic hazardous waste liquid, prevent pollution migration and diffusion of harmful substances such as heavy metals and the like, and improve the burning speed and the timely burnout rate of pulverized coal of a coal injection pipe of a main burner.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for cooperatively treating organic hazardous waste liquid by a cement kiln comprises the following steps:
(1) detoxification treatment: placing the organic hazardous waste liquid in a stirring tank, adding a detoxifying agent, stirring for 5-120 min, adding a heavy metal ion precipitator, stirring for 3-30 min, filtering and separating to obtain heavy metal precipitation filter residues and detoxified waste liquid;
(2) and (3) dehydration treatment: enabling the detoxified waste liquid obtained in the step (1) to flow through a dehydrating device loaded with granular or blocky or bagged dehydrating agents to obtain waste liquid fuel;
(3) and (3) cement kiln coprocessing: pumping the waste liquid fuel obtained in the step (2) as a fuel pump for supporting combustion of pulverized coal into a central fuel injection pipe of a kiln head coal injection pipe burner to be injected into a rotary kiln for combustion, and accelerating the oxidation combustion of the pulverized coal; or pumping the waste liquid fuel obtained in the step (2) into a central air pipe of a coal injection pipe burner of the kiln tail decomposing furnace to be injected into the decomposing furnace for combustion, thereby improving the combustion condition of the pulverized coal fuel in the decomposing furnace.
Further, in the step (1), the organic hazardous waste liquid is one or a mixture of more than two of hydrocarbon-containing hazardous waste liquid, organic solvent-containing waste, mineral oil-containing waste, oil-water waste, hydrocarbon/water mixture waste, emulsion waste and organic cyanide waste generated in chemical industry, medicine, dressing and metallurgy and mechanical processing.
Further, in the step (1), the detoxifying agent is at least one of ferrate, permanganate, percarbonate, soda ash, caustic soda, lime, hydrogen peroxide, chlorine dioxide and sodium/potassium thiosulfate. The detoxication agent can effectively eliminate the toxicity of substances with strong biological toxicity to medium biological toxicity, such as cyanide, in the heavy metal and/or halogenated hydrocarbon organic harmful waste liquid, eliminate volatile peculiar smell, convert soluble heavy metal into ionic state or dehalogenate in an oxidation mode, a reduction/complexation mode and/or a dehalogenation mode, and is beneficial to the subsequent heavy metal ion precipitation.
Further, in the step (1), the dosage of the detoxifying agent is 0.1-10%, preferably 1-8% of the mass of the organic hazard waste liquid.
Further, in the step (1), the heavy metal ion precipitating agent is an inorganic compound or an organic compound capable of effectively precipitating the corresponding heavy metal ion, and preferably phytic acid without biotoxicity. The heavy metal ion precipitator can capture and precipitate heavy metal ions in the heavy metal-containing organic hazardous waste liquid, so that the toxicity and the hazard are further reduced.
Further, in the step (1), the dosage of the heavy metal ion precipitator is 0.05-5%, preferably 1-3% of the mass of the heavy metal-containing organic hazardous waste liquid.
Further, in the step (1), the heavy metal precipitation filter residue can be electrolyzed to obtain heavy metal, and the heavy metal ion precipitator phytic acid is recycled.
Further, in the step (2), the dehydrating agent is at least one of silica gel, diatomite, quick lime, anhydrous sodium sulphate, calcined alum and clinker. The dehydrating agent deprives most of water from the organic hazardous waste liquid in an adsorption and/or hydration mode, and improves the combustibility of the subsequent cement kiln.
Further, the dehydrating agent is saturated and recycled, or is added into a kiln head cover (containing a rotary kiln cooling belt) of a cement plant for direct heat treatment and is converted into clinker or active blending material.
The invention has the beneficial effects that: (1) the process is simple, the investment is less, the strong biological toxicity of the hazardous waste liquid can be effectively eliminated, the heavy metal and/or dehalogenation can be efficiently enriched and removed, the high-heat-value liquid fuel with good combustion performance can be obtained, and no secondary pollution is caused; (2) hydrocarbon energy in the dangerous waste liquid can be effectively obtained, the flame temperature of the coal injection pipe burner can be directly increased, the oxidation combustion of the coal powder is accelerated, the timely burnout rate of the coal powder is increased, and the kiln condition of the cement kiln and the sintering quality of clinker are improved; the method is beneficial to clean resource utilization of the hazardous waste liquid containing hydrocarbon, promotes clean combustion of the coal powder entering the kiln, can effectively save fire coal, is beneficial to environmental protection, and is beneficial to the sustainable development of green, low-carbon and circular economy.
Detailed Description
The present invention will be further described with reference to the following examples.
The chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
The following examples of the present invention relate to criteria including: DB 37/T1939-2011 is used for solid wastes in cement production, GB 18597-2001 standard for controlling pollution of storage of dangerous wastes, Standard Corrosion differentiation of dangerous wastes (GB 5085.1-2007), Standard Leaching toxicity differentiation of dangerous wastes (GB 5085.3-2007), Standard general rules of identification of dangerous wastes (GB 5085.7), Standard content differentiation of toxic substances of hazardous wastes (GB 5085.6), Standard reactivity differentiation of hazardous wastes (GB 5085.5), Standard Specification of identification of hazardous wastes (HJ/T298), and TCLP experiment detection of clinker by using a toxicity characteristic Leaching method.
The following examples are all in a certain enterprise phi 4X 60m with five-stage cyclone preheater predecomposition kiln drying methodThe method is carried out on a cement production line, and during normal production, a kiln tail smoke chamber, a necking, moderate crust and a long ring are formed in a kiln, about 10 percent of reducing materials exist in clinker, and the stability of the kiln condition is deviated. The average output of clinker under normal kiln conditions is 2678t/d, the actual standard coal consumption of the clinker is 110.7kg/t, the vertical lifting weight fluctuation of the clinker is 1160-1330 g/L, the f-CaO fluctuation is 0.5-1.2%, the clinker strength fluctuation is 24.6-32.4 MPa in 3d compressive strength and 52.8-57.6 MPa in 28d compressive strength, the water requirement fluctuation of standard consistency is 23-28%, the fluctuation of condensation time is 104-137 min in initial setting and 139-168 min in final setting, and chloride ions (Cl) -) The content is 0.013%.
Example 1
In this embodiment, the liquid organic solvent-containing waste of a certain dangerous waste disposal company warehouse number category for HW06 is selected for use, and laboratory sampling detection: pH value of 6.5-8, water content of 67.3-74.8%, loss on ignition of 90.69-99.63%, SiO20.17～5.31%、Al2O30.02～0.11%、Fe2O30.01～0.14%、CaO 0.01～1.5%，MgO 0.00～0.05%、K2O 0.01～0.07%、Na20.01 to 0.42% of O, 0.04 to 1.16% of Cl, 0.01 to 0.05% of S, 0.01 to 1.05% of F, 0.03 to 0.11% of Cd, 0.03 to 0.09% of Pb, and 1878 to 2486Kcal/Kg of lower calorific value.
The detoxifying agent used in the embodiment is potassium ferrate and hydrogen peroxide, wherein the mass ratio of the potassium ferrate to the hydrogen peroxide is 1: 10; the heavy metal ion precipitator is phytic acid; the dehydrating agent is clinker produced by cement plant.
The present example was carried out as follows:
(1) detoxification treatment: placing the waste containing the organic solvent into a stirring tank, adding a detoxifying agent which accounts for 5% of the mass of the waste containing the organic solvent, stirring for reaction for 20min, oxidizing to remove strong biotoxicity of the waste containing the organic solvent, eliminating peculiar smell, and converting dissolved heavy metals into an ionic state; then adding a heavy metal ion precipitator which is equivalent to 0.9 percent of the mass of the organic solvent-containing waste under stirring, stirring for reaction for 10min until the heavy metal ions are completely precipitated, and filtering and separating to obtain heavy metal precipitation filter residues and detoxified waste liquid; collecting heavy metal precipitation filter residues, electrolyzing to prepare heavy metal, and recovering phytic acid;
(2) And (3) dehydration treatment: slowly flowing the detoxified waste liquid obtained in the step (1) through a granular dehydration device, and removing most of water to prepare a waste liquid fuel with the water content fluctuating between 0.5 and 3 percent; after the dehydrated saturated dehydrating agent clinker is recovered, directly performing heat treatment on a rotary kiln cooling belt thrown into a kiln head cover to convert the dehydrated saturated dehydrating agent clinker into clinker;
(3) and (3) cement kiln coprocessing: pumping the waste liquid fuel obtained in the step (2) into a central oil injection pipe of a kiln head coal injection pipe burner according to 9% of the mass of the coal dust of the head coal, injecting the waste liquid fuel into the rotary kiln for combustion, directly increasing the flame temperature of the coal injection pipe burner by the waste liquid fuel, accelerating the oxidation combustion of the coal dust, and increasing the timely burnout rate of the coal dust.
In order to track the fluctuation condition of the clinker quality, a round of clinker samples are taken every 2 hours.
The test is continuously operated for 72 hours, the combustion performance of the coal powder entering the kiln is obviously improved, the flame is powerful, the black fire head is shortened, the kiln condition is obviously improved, the preheater, a kiln tail smoke chamber, a throat and the kiln are not obviously skinned and stuck, the kiln head is clear and basically has no flying sand, the caking property of the clinker is good, the reducing material is reduced to about 2%, the fluctuation of the vertical lifting weight of the clinker is 1280-1380 g/L, the fluctuation of f-CaO is 0.5-1.0%, and the operation condition of the kiln system is normal. The kiln tail exhaust emission has no negative influence, and the environmental protection on-line flue gas monitoring shows SO 2The emission value and the denitration ammonia water consumption are equivalent.
3 days per ton of clinker raw coal consumption is reduced by 6.3 percent in the same ratio.
The clinker yield in 3 days is 2744t/d averagely, and is improved by 46 t/d.
The intensity fluctuation of the clinker is 32.8-34.9 MPa in 3d compressive strength and 57.4-60.4 MPa in 28d compressive strength, the water requirement fluctuation of the standard consistency is 22.5-26.5%, the fluctuation of the setting time is 100-124 min in initial setting and 127-147 min in final setting, and all physical and mechanical property indexes of the clinker are improved.
The material sample is cooked for 3 days, the detected content fluctuation of the chloride ions is 0.012-0.014%, and the content fluctuation is all lower than the standard that the chloride ions in the cement industry are less than 0.06%.
3-day detection of clinker sample TCLP experiment: chromium, lead, mercury, zinc, cadmium and arsenic are all 0.00mg/kg, and heavy metals are completely and fixedly dissolved in aluminosilicate mineral crystal lattices.
The production test shows that the method for cooperatively treating the organic hazardous waste liquid by the cement kiln can effectively remove strong biotoxicity of the organic hazardous waste liquid, eliminate foreign odor, remove heavy metals, dehydrate and convert the heavy metals into nontoxic hydrocarbon fuel, can effectively promote pulverized coal combustion, improve burnout rate, improve the working condition of the kiln system, has positive influence on kiln conditions and clinker combustion quality, can effectively save part of fire coal, and has no negative influence on kiln tail smoke emission.
Example 2
The embodiment selects the liquid mineral oil-containing waste with the warehouse number category of a certain dangerous waste disposal company being HW08, and the laboratory sampling detection: pH value of 6.7-8, water content of 75-78%, loss on ignition of 92.64-94.74%, SiO20.37～4.31%、Al2O30.42～2.59%、Fe2O3.23～1.58%、CaO 0.41～0.51%、MgO 0.04～0.25%、K2O 0.02～0.05%、Na20.09-0.16% of O, 0.04-0.18% of Cl, 0.03-0.87% of S, 0.01-0.02% of F, 0.04-0.19% of Cd, 0.61-3.23% of Pb and 1487-2219 Kcal/Kg of low calorific value.
The detoxifying agent used in the embodiment is potassium ferrate and chlorine dioxide, wherein the mass ratio of the potassium ferrate to the chlorine dioxide is 1: 13; the heavy metal ion precipitator is phytic acid; the dehydrating agent is clinker produced by cement plant.
The present example was carried out as follows:
(1) detoxification treatment: placing the mineral oil-containing waste into a stirring tank, adding a detoxifying agent which accounts for 5.7% of the mass of the mineral oil-containing waste, stirring for reacting for 40min, oxidizing to remove strong biotoxicity of the mineral oil-containing waste, eliminating peculiar smell, and converting dissolved heavy metals into ionic state; then, adding a heavy metal ion precipitator which is equivalent to 1.2 percent of the mass of the mineral oil-containing waste under stirring, stirring and reacting for 20min until the heavy metal ions are completely precipitated, and filtering and separating to obtain heavy metal precipitation filter residues and detoxified waste liquid; collecting heavy metal filter residues, electrolyzing to prepare heavy metal, and recovering phytic acid;
(2) And (3) dehydration treatment: slowly flowing the detoxified waste liquid obtained in the step (1) through a dehydrating device loaded with granular or blocky or bagged dehydrating agents, and then removing most of water to prepare a waste liquid fuel with the water content fluctuation of 3.3-5.4%; after the dehydrated saturated dehydrating agent clinker is recovered, directly performing heat treatment on a rotary kiln cooling belt thrown into a kiln head cover to convert the dehydrated saturated dehydrating agent clinker into clinker;
(3) and (3) cement kiln coprocessing: pumping the waste liquid fuel obtained in the step (2) into a central oil injection pipe of a kiln head coal injection pipe burner according to 23% of the mass of the coal dust, injecting the waste liquid fuel into the rotary kiln for combustion, directly increasing the flame temperature of the coal injection pipe burner by the waste liquid fuel, accelerating the oxidation combustion of the coal dust, and increasing the timely burnout rate of the coal dust.
In order to track the fluctuation condition of the clinker quality, a round of clinker samples are taken every 2 hours.
The test is continuously operated for 72 hours, the combustion performance of the coal powder entering the kiln is obviously improved, the flame is powerful, the black fire head is shortened, the kiln condition is obviously improved, the preheater, a kiln tail smoke chamber, a throat and the kiln are not obviously skinned and stuck, the kiln head is clear and basically has no flying sand, the caking property of the clinker is good, the reducing material is reduced to about 2%, the fluctuation of the vertical lifting weight of the clinker is 1280-1380 g/L, the fluctuation of f-CaO is 0.5-1.0%, and the operation condition of the kiln system is normal. The kiln tail exhaust emission does not have any negative effect, and the environmental protection on-line flue gas monitoring shows that the SO2 emission value and the denitration ammonia water consumption are equivalent.
The raw coal consumption of 3 days per ton of clinker is reduced by 12.9 percent.
The clinker yield in 3 days is 2757t/d averagely, and is improved by 59 t/d.
The intensity fluctuation of the clinker is 32.8-35.0 MPa in 3d compressive strength and 57.4-60.8 MPa in 28d compressive strength, the water requirement fluctuation of the standard consistency is 22.5-26.5%, the fluctuation of the setting time is 100-124 min in initial setting and 127-147 min in final setting, and all physical and mechanical property indexes of the clinker are improved.
The material sample is cooked for 3 days, the detected content fluctuation of the chloride ions is 0.014-0.017%, and the content fluctuation is all lower than the standard that the chloride ions in the cement industry are less than 0.06%.
3-day detection of clinker sample TCLP experiment: chromium, lead, mercury, zinc, cadmium and arsenic are all 0.00mg/kg, and heavy metals are completely and fixedly dissolved in aluminosilicate mineral crystal lattices.
The production test shows that the method for cooperatively treating the organic hazardous waste liquid by the cement kiln can effectively remove strong biotoxicity of the organic hazardous waste liquid, eliminate foreign odor, remove heavy metals, dehydrate and convert the heavy metals into nontoxic hydrocarbon fuel, can effectively promote pulverized coal combustion, improve burnout rate, improve the working condition of the kiln system, has positive influence on kiln conditions and clinker combustion quality, can effectively save part of fire coal, and has no negative influence on kiln tail smoke emission.
Example 3
This embodiment selects liquid (emulsion) waste that a certain danger was wasted disposal company warehouse serial number classification is HW09, laboratory sampling test: pH value of 7.5-8.5, water content of 68.7-73.6%, loss on ignition of 98.94-99.48%, SiO20.01～0.04%、Al2O30.01～0.09%、Fe2O30.01～0.09%、CaO 0.02～0.22%、MgO 0.01～0.11%、K2O 0.01～0.05%、Na20.01-0.04% of O, 0.04-0.08% of Cl, 0.03-0.11% of S, 0.00-0.02% of F, 0.03-0.09% of Cd, 0.03-0.09% of Pb and 1487-2219 Kcal/Kg of low calorific value.
The detoxifying agent used in the embodiment is sodium percarbonate and chlorine dioxide, and the application mass ratio of the sodium percarbonate to the chlorine dioxide is 1:10, and the sodium percarbonate and the chlorine dioxide are directly applied; the heavy metal ion precipitator is phytic acid; the dehydrating agent is clinker produced by cement plant.
The present example was carried out as follows:
(1) detoxification treatment: putting the liquid (emulsion) waste into a stirring tank, adding a detoxifying agent which accounts for 2.2% of the mass of the liquid (emulsion) waste, stirring for reacting for 40min, oxidizing to remove strong biotoxicity of the liquid (emulsion) waste, eliminating peculiar smell, and converting dissolved heavy metals into ionic state; then, adding a heavy metal ion precipitator which is 0.6 percent of the mass of the liquid (emulsion) waste under stirring, stirring and reacting for 20min until the heavy metal ions are completely precipitated, and filtering and separating to obtain heavy metal filter residue and detoxified waste liquid;
(2) And (3) dehydration treatment: slowly flowing the detoxified waste liquid obtained in the step (1) through a dehydrating device loaded with granular or blocky or bagged dehydrating agents, and then removing most of water to prepare a waste liquid fuel with the water content fluctuation of 2.9-4.7%; after the dehydrated saturated dehydrating agent clinker is recovered, directly performing heat treatment on a rotary kiln cooling belt thrown into a kiln head cover to convert the dehydrated saturated dehydrating agent clinker into clinker;
(3) and (3) cement kiln coprocessing: and (3) pumping the waste liquid fuel obtained in the step (2) into a central oil injection pipe of a kiln head coal injection pipe burner to be injected into the rotary kiln to be combusted according to 35% of the mass of the first tail coal powder, and feeding the waste liquid fuel into a decomposing furnace to be combusted in a central air pipe of 2 tail coal injection pipes.
In order to track the fluctuation condition of the clinker quality, a round of clinker samples are taken every 2 hours.
The test is continuously operated for 72 hours, the combustion performance of the coal powder entering the kiln is obviously improved, the flame is powerful, the black fire head is shortened, the kiln condition is obviously improved, the preheater, a kiln tail smoke chamber, a throat and the kiln are not obviously skinned and stuck, the kiln head is clear and basically has no flying sand, the caking property of the clinker is good, the reducing material is reduced to about 2%, the fluctuation of the vertical lifting weight of the clinker is 1280-1380 g/L, the fluctuation of f-CaO is 0.5-1.0%, and the operation condition of the kiln system is normal. The kiln tail exhaust emission has no negative influence, and the environmental protection on-line flue gas monitoring shows SO 2The emission value and the denitration ammonia water consumption are equivalent.
The raw coal consumption of 3 days per ton of clinker is reduced by 41.3 percent.
The clinker yield in 3 days is 2819t/d averagely, and is improved by 121 t/d.
The intensity fluctuation of the clinker is 33.8-36.4 MPa in 3d compressive strength and 58.7-60.8 MPa in 28d compressive strength, the water requirement fluctuation of the standard consistency is 22.5-26.5%, the fluctuation of the setting time is 100-124 min in initial setting and 127-147 min in final setting, and all physical and mechanical performance indexes of the clinker are improved.
The material sample is cooked for 3 days, the detected content fluctuation of the chloride ions is 0.013-0.015 percent, and the detected content fluctuation is all lower than the standard that the chloride ions in the cement industry are less than 0.06 percent.
3-day detection of clinker sample TCLP experiment: chromium, lead, mercury, zinc, cadmium and arsenic are all 0.00mg/kg, and heavy metals are completely and fixedly dissolved in aluminosilicate mineral crystal lattices.
The production test shows that the method for cooperatively treating the organic hazardous waste liquid by the cement kiln can effectively remove strong biotoxicity of the organic hazardous waste liquid, eliminate foreign odor, remove heavy metals, dehydrate and convert the heavy metals into nontoxic hydrocarbon fuel, can effectively promote pulverized coal combustion, improve burnout rate, improve the working condition of the kiln system, has positive influence on kiln conditions and clinker combustion quality, can effectively save part of fire coal, and has no negative influence on kiln tail smoke emission.
Example 4
In the embodiment, the liquid waste with the warehouse number of HW11 of a certain dangerous waste disposal company is selected, and the laboratory sampling detection is the harmful waste liquid mainly comprising the alcohol amine desulfurization waste liquid of an oil refinery, the liquid waste has peculiar smell, the pH value is 6-7, the water content is 47.4-68.5%, the ignition loss is 97.35-98.74%, and the SiO is20.23～0.63%、Al2O30.14～0.67%、Fe2O30.01～0.09%、CaO 0.31～0.72%、MgO 0.01～0.11%、K2O 0.37～0.53%、Na20.13 to 0.25% of O, 0.22 to 0.31% of Cl, 2.96 to 4.76% of S, 0.00 to 0.02% of F, 0.14 to 0.22% of Cd, 0.16 to 0.37% of Pb, and 1943 to 3974Kcal/Kg of lower calorific value.
In the embodiment, sodium thiosulfate is selected as the detoxifying agent; the heavy metal ion precipitator is phytic acid; the dehydrating agent is clinker produced by cement plant.
The present example was carried out as follows:
(1) detoxification treatment: putting the liquid waste into a stirring tank, adding a detoxifying agent which accounts for 4.7% of the mass of the liquid waste, stirring and reacting for 70min to remove the strong biotoxicity of the liquid waste by strong reduction, eliminate the foreign odor and convert the dissolved heavy metal into a complex state; then, adding a heavy metal ion precipitator which is 1.3 percent of the mass of the liquid waste under stirring, stirring and reacting for 30min until the heavy metal ions are completely precipitated, and filtering and separating to obtain heavy metal precipitation filter residues and detoxified waste liquid;
(2) and (3) dehydration treatment: slowly flowing the detoxified waste liquid obtained in the step (1) through a dehydrating device loaded with granular or blocky or bagged dehydrating agents, and then removing most of water to prepare a waste liquid fuel with the water content fluctuation of 3.6-4.9%; after the dehydrated saturated dehydrating agent clinker is recovered, directly performing heat treatment on a rotary kiln cooling belt thrown into a kiln head cover to convert the dehydrated saturated dehydrating agent clinker into clinker;
(3) And (3) cement kiln coprocessing: and (3) pumping the waste liquid fuel obtained in the step (2) into a central oil injection pipe of a kiln head coal injection pipe burner to be injected into the rotary kiln to be combusted according to 37% of the mass of the first tail coal powder, and feeding the waste liquid fuel into a decomposing furnace to be combusted in a central air pipe of 2 tail coal injection pipes.
In order to track the fluctuation condition of the clinker quality, a round of clinker samples are taken every 2 hours.
The test is continuously operated for 72 hours, the combustion performance of the coal powder entering the kiln is obviously improved, the flame is powerful, the black fire head is shortened, the kiln condition is obviously improved, the preheater, a kiln tail smoke chamber, a throat and the kiln are not obviously skinned and stuck, the kiln head is clear and basically has no flying sand, the caking property of the clinker is good, the reducing material is reduced to about 2%, the fluctuation of the vertical lifting weight of the clinker is 1280-1380 g/L, the fluctuation of f-CaO is 0.5-1.0%, and the operation condition of the kiln system is normal. The kiln tail exhaust emission does not have any negative effect, and the environmental protection on-line flue gas monitoring shows that the SO2 emission value and the denitration ammonia water consumption are equivalent.
3 days per ton of clinker raw coal consumption is reduced by 48.9 percent in the same ratio.
The clinker yield in 3 days is 2821t/d averagely, and 123t/d is improved.
The intensity fluctuation of the clinker is 34.2-36.9 MPa in 3d compressive strength and 58.9-64.1 MPa in 28d compressive strength, the water requirement fluctuation of the standard consistency is 22.5-26.5%, the fluctuation of the setting time is 100-122 min in initial setting and 127-149 min in final setting, and all physical and mechanical performance indexes of the clinker are improved.
The material sample is cooked for 3 days, the detected content fluctuation of the chloride ions is 0.014-0.017%, and the content fluctuation is all lower than the standard that the chloride ions in the cement industry are less than 0.06%.
3-day detection of clinker sample TCLP experiment: chromium, lead, mercury, zinc, cadmium and arsenic are all 0.00mg/kg, and heavy metals are completely and fixedly dissolved in aluminosilicate mineral crystal lattices.
The production test shows that the method for cooperatively treating the organic hazardous waste liquid by the cement kiln can effectively remove strong biotoxicity of the organic hazardous waste liquid, eliminate foreign odor, remove heavy metals, dehydrate and convert the heavy metals into nontoxic hydrocarbon fuel, can effectively promote pulverized coal combustion, improve burnout rate, improve the working condition of the kiln system, has positive influence on kiln conditions and clinker combustion quality, can effectively save part of fire coal, and has no negative influence on kiln tail smoke emission.
Example 5
In this embodiment, the liquid organic solvent-containing waste of a certain dangerous waste disposal company warehouse number category for HW06 is selected for use, and laboratory sampling detection: pH value of 6.5-7.5, moisture of 58.7-66.9%, loss on ignition of 90.36-97.35%, SiO21.64～4.33%、Al2O30.21～0.47%、Fe2O30.06～0.19%、CaO 1.0～1.7%，MgO 0.03～0.08%、K2O 0.13～0.24%、Na20.26 to 0.40% of O, 0.16 to 0.76% of Cl, 0.14 to 0.35% of S, 0.23 to 0.74% of F, 0.13 to 0.31% of Cd, 0.22 to 0.37% of Pb, and 2387 to 3367Kcal/Kg of lower calorific value.
The detoxifying agent used in the embodiment is potassium ferrate and hydrogen peroxide, wherein the mass ratio of the potassium ferrate to the hydrogen peroxide is 1: 15; the heavy metal ion precipitator is phytic acid; the dehydrating agent is clinker produced by cement plant.
The present example was carried out as follows:
(1) detoxification treatment: placing the waste containing the organic solvent into a stirring tank, adding a detoxifying agent which accounts for 5% of the mass of the waste containing the organic solvent, stirring for reaction for 30min, oxidizing to remove strong biotoxicity of the waste containing the organic solvent, eliminating peculiar smell, and converting dissolved heavy metals into an ionic state; then adding a heavy metal ion precipitator which is equivalent to 2.7 percent of the mass of the organic solvent-containing waste under stirring, stirring and reacting for 30min until the heavy metal ions are completely precipitated, and filtering and separating to obtain heavy metal precipitation filter residues and detoxified waste liquid;
(2) and (3) dehydration treatment: slowly flowing the detoxified waste liquid obtained in the step (1) through a dehydrating device loaded with a blocky dehydrating agent, and then removing most of water to prepare a waste liquid fuel with the water content fluctuating between 2.3 and 4.6 percent; after the dehydrated saturated dehydrating agent clinker is recovered, directly performing heat treatment on a rotary kiln cooling belt thrown into a kiln head cover to convert the dehydrated saturated dehydrating agent clinker into clinker;
(3) and (3) cement kiln coprocessing: and (3) pumping the waste liquid fuel obtained in the step (2) into a central oil injection pipe of a kiln head coal injection pipe burner according to 7.3% of the mass of the head coal powder to be sprayed into the rotary kiln for burning.
In order to track the fluctuation condition of the clinker quality, a round of clinker samples are taken every 2 hours.
The test is continuously operated for 72 hours, the combustion performance of the coal powder entering the kiln is obviously improved, the flame is powerful, the black fire head is shortened, the kiln condition is obviously improved, the preheater, a kiln tail smoke chamber, a throat and the kiln are not obviously skinned and stuck, the kiln head is clear and basically has no flying sand, the caking property of the clinker is good, the reducing material is reduced to about 2%, the fluctuation of the vertical lifting weight of the clinker is 1280-1380 g/L, the fluctuation of f-CaO is 0.5-1.0%, and the operation condition of the kiln system is normal. The kiln tail exhaust emission has no negative influence, and the environmental protection on-line flue gas monitoring shows SO2The emission value and the denitration ammonia water consumption are equivalent.
3 days per ton of clinker raw coal consumption is reduced by 4.9 percent in the same ratio.
The clinker yield in 3 days is 2749t/d averagely, and is improved by 51 t/d.
The intensity fluctuation of the clinker is 33.7-34.6 MPa in 3d compressive strength and 57.8-60.7 MPa in 28d compressive strength, the water requirement fluctuation of the standard consistency is 22.5-26.5%, the fluctuation of the setting time is 100-119 min in initial setting and 127-146 min in final setting, and all physical and mechanical performance indexes of the clinker are improved.
The material sample is cooked for 3 days, the detected content fluctuation of the chloride ions is 0.013-0.019%, and the detected content fluctuation is all lower than the standard that the chloride ions in the cement industry are less than 0.06%.
3-day detection of clinker sample TCLP experiment: chromium, lead, mercury, zinc, cadmium and arsenic are all 0.00mg/kg, and heavy metals are completely and fixedly dissolved in aluminosilicate mineral crystal lattices.
The production test shows that the method for cooperatively treating the organic hazardous waste liquid by the cement kiln can effectively remove strong biotoxicity of the organic hazardous waste liquid, eliminate foreign odor, remove heavy metals, dehydrate and convert the heavy metals into nontoxic hydrocarbon fuel, can effectively promote pulverized coal combustion, improve burnout rate, improve the working condition of the kiln system, has positive influence on kiln conditions and clinker combustion quality, can effectively save part of fire coal, and has no negative influence on kiln tail smoke emission.
Claims (9)
1. A method for cooperatively treating organic hazardous waste liquid by a cement kiln is characterized by comprising the following steps:
(1) detoxification treatment: placing the organic hazardous waste liquid in a stirring tank, adding a detoxifying agent, stirring for 5-120 min, adding a heavy metal ion precipitator, stirring for 3-30 min, filtering and separating to obtain heavy metal precipitation filter residues and detoxified waste liquid;
(2) and (3) dehydration treatment: enabling the detoxified waste liquid obtained in the step (1) to flow through a dehydrating device loaded with granular or blocky or bagged dehydrating agents to obtain waste liquid fuel;
(3) and (3) cement kiln coprocessing: pumping the waste liquid fuel obtained in the step (2) as a fuel pump for supporting combustion of pulverized coal into a central fuel injection pipe of a kiln head coal injection pipe burner to be injected into a rotary kiln for combustion, and accelerating the oxidation combustion of the pulverized coal; or pumping the waste liquid fuel obtained in the step (2) into a central air pipe of a coal injection pipe burner of the kiln tail decomposing furnace to be injected into the decomposing furnace for combustion, thereby improving the combustion condition of the pulverized coal fuel in the decomposing furnace.
2. The method for the synergistic treatment of the organic hazardous waste liquid by the cement kiln as claimed in claim 1, wherein in step (1), the organic hazardous waste liquid is one or a mixture of more than two of hydrocarbon-containing hazardous waste liquid, organic solvent-containing waste, mineral oil-containing waste, oil-water waste, hydrocarbon/water mixture waste, emulsion waste and organic cyanide waste generated in chemical, pharmaceutical, metallurgical and mechanical processing.
3. The method for the synergistic treatment of the organic hazardous waste liquid by the cement kiln as claimed in claim 1 or 2, wherein in step (1), the detoxifying agent is at least one of ferrate, permanganate, percarbonate, soda ash, caustic soda, lime, hydrogen peroxide, chlorine dioxide and sodium/potassium thiosulfate.
4. The method for the synergistic treatment of the organic hazardous waste liquid by the cement kiln according to one of the claims 1 to 3, wherein in the step (1), the dosage of the detoxifying agent is 0.1 to 10 percent, preferably 1 to 8 percent of the mass of the organic hazardous waste liquid.
5. The method for the synergistic treatment of the waste liquid containing the heavy metal organic hazard in the cement kiln as claimed in one of claims 1 to 4, wherein in the step (1), the heavy metal ion precipitator is preferably phytic acid.
6. The method for the synergistic treatment of the organic hazardous waste liquid by the cement kiln according to one of the claims 1 to 5, wherein in the step (1), the amount of the heavy metal ion precipitator is 0.05 to 5 percent, preferably 1 to 3 percent of the mass of the organic hazardous waste liquid.
7. The method for the synergistic treatment of the organic hazardous waste liquid by the cement kiln according to any one of claims 1 to 6, wherein in the step (1), the heavy metal precipitation filter residue is electrolyzed to obtain heavy metal, and the heavy metal ion precipitator is recovered for recycling.
8. The method for the synergistic treatment of the organic hazardous waste liquid by the cement kiln according to one of the claims 1 to 7, wherein in the step (2), at least one of dehydrating agent silica gel, diatomite, quicklime, anhydrous sodium sulphate, calcined alum and clinker is adopted.
9. The method for the cooperative treatment of the organic hazardous waste liquid by the cement kiln as claimed in claim 8, wherein the dehydrating agent is saturated and recycled, or added into a kiln head hood (including a cooling belt of the rotary kiln) of a cement plant to be directly converted into clinker or active blending material by heat treatment.
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