CN112973411A - Process and device for producing ammonium sulfite and byproduct thiosulfate mixed nutrient solution - Google Patents
Process and device for producing ammonium sulfite and byproduct thiosulfate mixed nutrient solution Download PDFInfo
- Publication number
- CN112973411A CN112973411A CN202110364172.7A CN202110364172A CN112973411A CN 112973411 A CN112973411 A CN 112973411A CN 202110364172 A CN202110364172 A CN 202110364172A CN 112973411 A CN112973411 A CN 112973411A
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- Prior art keywords
- absorption tower
- nutrient solution
- tower
- mixed nutrient
- sulfur
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- 235000015097 nutrients Nutrition 0.000 title claims abstract description 153
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 49
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 28
- 239000006227 byproduct Substances 0.000 title abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 234
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 166
- 239000011593 sulfur Substances 0.000 claims abstract description 143
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 143
- 238000005406 washing Methods 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000003546 flue gas Substances 0.000 claims abstract description 59
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 42
- 239000007787 solid Substances 0.000 claims abstract description 41
- 239000003513 alkali Substances 0.000 claims abstract description 34
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 239000000428 dust Substances 0.000 claims abstract description 13
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 133
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 63
- 238000007872 degassing Methods 0.000 claims description 35
- 239000003337 fertilizer Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 33
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 32
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 28
- 239000007921 spray Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims description 21
- 238000002485 combustion reaction Methods 0.000 claims description 19
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 19
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 19
- 238000000746 purification Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 238000006477 desulfuration reaction Methods 0.000 claims description 14
- 230000023556 desulfurization Effects 0.000 claims description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 10
- 239000000347 magnesium hydroxide Substances 0.000 claims description 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- 239000000779 smoke Substances 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 239000000618 nitrogen fertilizer Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000002686 phosphate fertilizer Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 200
- 238000007280 thionation reaction Methods 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 59
- 229910021529 ammonia Inorganic materials 0.000 description 23
- 239000012535 impurity Substances 0.000 description 17
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000002893 slag Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000003009 desulfurizing effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000006378 damage Effects 0.000 description 6
- 235000010265 sodium sulphite Nutrition 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 4
- 239000000567 combustion gas Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000382 dechlorinating effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 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 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000729 antidote Substances 0.000 description 1
- 229940075522 antidotes Drugs 0.000 description 1
- ASPXBYAQZVXSNS-UHFFFAOYSA-N azane;sulfurous acid;hydrate Chemical compound N.N.O.OS(O)=O ASPXBYAQZVXSNS-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- -1 charcoal Chemical compound 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 239000000988 sulfur dye Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Images
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
- B01D50/40—Combinations of devices covered by groups B01D45/00 and B01D47/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
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- B01D—SEPARATION
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- B01D53/73—After-treatment of removed components
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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- B01D—SEPARATION
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/79—Injecting reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/64—Thiosulfates; Dithionites; Polythionates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/14—Preparation of sulfites
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
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- B01D2251/512—Phosphoric acid
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Abstract
The invention discloses a process and a device for producing ammonium sulfite and by-producing a thiosulfate mixed nutrient solution, wherein solid matters rich in sulfur are combusted, generated flue gas enters a cyclone separation tower for dust removal, and the flue gas after dust removal enters a heat exchanger for cooling; then the flue gas enters a washing and purifying tower for washing; the flue gas enters a primary absorption tower, a secondary absorption tower and a tertiary absorption tower respectively for absorption, the obtained liquid is crystallized by cooling, and solid ammonium sulfite is separated by a centrifugal machine in a neutralization tank; liquid in the washing and purifying tower and residual liquid in the neutralizing tank enter a mixed nutrient solution generating kettle to perform a thionation reaction to generate a thiosulfate mixed nutrient solution, and acid or alkali is added into the solution in the mixed nutrient solution generating kettle to adjust the pH value of the mixed nutrient solution; the flue gas enters a water washing tower to be washed and then is discharged. The method can obtain high-purity solid ammonium sulfite and byproduct thiosulfate mixed nutrient solution, and has good special industrial application and prospect.
Description
Technical Field
The invention relates to a process and a device for producing mixed nutrient solution, in particular to a process and a device for producing ammonium sulfite and by-producing thiosulfate mixed nutrient solution.
Background
Sodium thiosulfate, also known as sodium bicarbonate and seawave are monoclinic white crystalline powder, are easily soluble in water and insoluble in alcohol, and are mainly used as reducing agents in the manufacturing of tetraethyl lead, dye intermediates and the like, electroplating industries of ore silver extraction and the like, and water purifying agents in water purification engineering. Dechlorinating agents for bleaching cotton fabrics in textile industry, sulfur dyes for dyeing wool fabrics, anti-whitening agents for indigo dyes, pulp dechlorinating agents, detergents, disinfectants and color fading agents in pharmaceutical industry, analytical reagents for chromatography, cobalt determination by drop analysis, photographic fixing agents, common reagents for dechlorinating agent volumetric analysis, blood sodium determination, preparation of injections and met-al medium, mordant, sodium thiosulfate are used as antidotes for cyanide.
The patent with publication number CN103788960A discloses a functional fertilizer and a repairing agent for repairing soil heavy metals, wherein modified attapulgite, chitosan, biochar and sodium thiosulfate are compounded, so that on one hand, the adsorption performance of the attapulgite and the biochar and the chelation effect of the chitosan are utilized to fix heavy metal ions in soil and prevent the heavy metal ions from being leached and migrated by runoff; on one hand, sodium thiosulfate is used for reducing high-valence heavy metal ions (such as hexavalent chromium ions) into low-valence states (such as trivalent chromium ions), so that the toxicity and the solubility of the heavy metal ions are reduced. The thiosulfate can also be used as an additive of a fertilizer, can be used together with a conventional chemical fertilizer and a compound fertilizer, and has better fertilizer efficiency.
Patent publication No. CN106809807A discloses a method for preparing sodium thiosulfate, which comprises preparing a mixed solution of sodium sulfite and sodium hydroxide, heating the sodium thiosulfate solution, stirring, filtering while hot, heating in a steam bath for evaporation, cooling, filtering under reduced pressure, and crystallizing. The method comprises the steps of reacting a sodium hydroxide solution with the molar concentration of 1mol/L with sulfur dioxide gas to generate a mixed solution, heating and mixing the reacted mixed solution with sulfur powder under the conditions that the pH =11 and the temperature is 101 ℃, adding activated carbon powder after 27min, stirring, filtering while hot, heating and evaporating in nitrogen airflow, cooling, crystallizing and drying.
The patent with publication number CN101891159A discloses a preparation method of analytically pure sodium thiosulfate, which comprises the steps of (1) placing distilled water and sodium sulfite into a stainless steel reactor, heating for dissolving, heating the solution to boiling after dissolving, slowly adding sulfur powder into the stainless steel reactor, boiling the reaction mixture for 2-3 hours until the solution is no longer alkaline, stopping heating, standing for 5-6 hours, and filtering to obtain a solution A; (2) heating and concentrating the solution A, concentrating the solution to 22-23 DEG Be, cooling to obtain crystals, transferring the crystals into a vacuum drier for drying at the temperature of 30-35 ℃, and taking out to obtain an analytically pure sodium thiosulfate finished product. The method synthesizes the sodium sulfite and the sulfur powder to obtain the analytically pure sodium thiosulfate, has simple process steps, easy operation control and high production efficiency, and the prepared sodium thiosulfate has low impurity content, so that the product can be widely applied in the market.
Patent publication No. CN106430114A discloses a method for producing sodium thiosulfate pentahydrate, which is characterized by comprising the following steps: (1) adding water into the slag containing the elemental sulfur, and stirring, washing, filtering and separating to obtain a filter cake A and a filtrate A; (2) adding sodium sulfite and water into the filter cake A, wherein the addition of the sodium sulfite is 1.1-1.2 times of the theoretical value, and the addition of the water is 15-20 times of the slag material containing the elemental sulfur, and heating, stirring and leaching the mixed material; then filtering and washing are carried out to obtain a filter cake B containing noble metal and a filtrate B; and evaporating, cooling, crystallizing, overflowing, filtering, separating and drying the filtrate B to obtain the sodium thiosulfate pentahydrate. The invention effectively recovers valuable elements and obtains two products of sodium thiosulfate pentahydrate and sodium sulfate.
The patent with publication number CN104071759A discloses a novel preparation method of sodium thiosulfate, which relates to the technical field of chemical industry, and comprises the steps of selecting qualified soda ash, adding water, uniformly stirring and mixing, adding sulfur dioxide, reacting to obtain a sodium sulfite solution, putting into a high-pressure reaction kettle, continuously stirring, heating until the solution boils, adding sulfur, continuously stirring and heating for 1.5 hours to obtain a hot solution, and conveying into an oxidation reaction kettle to control the temperature in the kettle to be 70-80 ℃ for oxidation reaction. And (3) when the reactant turns yellow or white, inputting the solution into an evaporation kettle for evaporation, decoloring the activated carbon, performing filter pressing, cooling, crystallizing, centrifuging by using a centrifugal machine, screening out industrial-grade sodium thiosulfate, putting the industrial-grade sodium thiosulfate into the crystallization kettle again for recrystallization to obtain a sodium thiosulfate finished product, and packaging and warehousing the sodium thiosulfate finished product. The invention has the beneficial effects that: the method has the advantages of convenient and simple preparation, environmental protection, no pollution, less equipment investment, high purity, convenient operation, good use effect of the prepared sodium thiosulfate, safety and reliability.
In the prior art, the production process of thiosulfate comprises the steps of thionation, oxidation, evaporation, crystallization and the like, and is characterized in that a dilute sodium sulfide solution is concentrated to prepare a concentrated solution, the concentrated solution reacts with sulfur at a certain temperature to generate a sodium polysulfide solution, then air blowing is carried out to oxidize the sodium polysulfide solution to generate a dilute sodium bicarbonate solution, and a series of steps of evaporation, concentration, crystallization and the like are carried out to prepare a finished product. The existing thiosulfate preparation method has complex process, difficult control of the reaction process and serious pollution and waste. In addition, Chinese sulfur has high dependence on the outside, and the sulfur price is high. The Chinese sulfur yield, the imported quantity and the market data in 2019, the Chinese sulfur yield in 2019 is about 7440 kt, the year-by-year increase is 9.4%, the imported sulfur quantity is 11730 kt, the year-by-year increase is 8.8%, the Chinese imported Japan in 2019 has the Korean liquid sulfur quantity of 2039.9 kt, the Korean liquid sulfur quantity is basically equal to that in 2018, the Chinese sulfur market in 2019 is low all the way, the annual reduction amplitude is 50%, in the process, new records are repeatedly brushed on related data, the average value of sulfur in ports in China in 2019 reaches 1890 kt, the national sulfur yield in China in 2750 kt.2020 continues to be expected to increase, the imported quantity probably needs to see the overall performance of the port inventory consumption and the downstream, and comprehensively, the pressure borne by the sulfur market in 2020 is not less than the previous years. Due to the restriction of the factors, the currently produced thiosulfate fertilizer has high cost, the price is 6-10 times of that of the fertilizer represented by ammonium sulfate, and the application of the thiosulfate fertilizer in the aspect of agricultural fertilizers is limited due to the overhigh price.
The waste sulfur source treatment of high-energy-consumption enterprises in China is always the problem of headache of the enterprises. The waste sulfur sources mainly come from: black sulfur in a coking plant, secondary sulfur in a chemical fertilizer plant, sulfur filtration sulfur slag in a sulfuric acid plant, sulfur slag desulfurized by carbon disulfide, industrial defective sulfur, sulfur slag, sulfur mud, sulfur paste and the like. These substances themselves have a great environmental pollution and the emissions are restricted by national policies. Due to the low grade of the raw materials, if advanced equipment and processes are not provided, the investment for enterprises to use is very large, the income is very low, and if only special recycling items are provided on the waste resources, the risk is very large, and the investment is very high.
Ammonium sulfite is an important chemical product (the chemical industry standard of the people's republic of China, industrial ammonium sulfite, HG/T2784-1996), is a chemical fertilizer and a chemical agent, has larger and larger demand along with the popularization of the pulping process of the ammonium sulfite method, and plays a larger and larger role in the improvement of the traditional paper making industry.
Ammonium sulfite is one of the most common by-products of ammonia desulfurization technology. The ammonia desulfurization technology is to remove SO in flue gas by adopting ammonia as an absorbent2The process of (1). The ammonia desulphurization process has many characteristics, firstly, ammonia is a good alkaline absorbent, the alkalinity is stronger than that of a calcium-based absorbent, and the ammonia absorbs sulfur dioxide in flue gas through gas-gas reaction or gas-liquid reaction, so that the reaction speed is high, the reaction is complete, the utilization rate of the absorbent is high, and the high desulphurization efficiency can be obtained. Compared with the calcium-based desulfurization process, the ammonia desulfurization system is simple and the equipment volume is smallSmall and no secondary pollution, and in addition, the desulphurization byproduct ammonium sulfate is a common chemical fertilizer, and the sales income of the byproduct can greatly improve the economic benefit.
When coal gangue, sulfur-containing minerals and the like are combusted, the discharged flue gas contains SO2. SO in flue gas2The content is usually low, typically between 300-. In the case of coal-fired boilers, the steam scale is from 1T/h to 2500T/h, the generator set capacity is from 6MW to 900MW, and the flue gas amount is from 1 ten thousand Nm3H to 250 ten thousand Nm3H, severe acid rain and SO have been generated2And (4) pollution. The ammonia desulphurization technology is to remove SO in the flue gas2The by-products are sulfuric acid, ammonium sulfate fertilizer and ammonium sulfite. The ammonia desulphurization technology can produce the commonly used solid ammonium sulfite, but because of SO in the flue gas2The content is generally lower and the quality of the produced product is lower.
In addition, the traditional desulfurization device adopting the ammonia desulfurization technology is a two-stage desulfurization tower, and the device is suitable for the gas which is self-smoke of factory tail gas and is not suitable for high-concentration sulfur dioxide gas generated by burning auxiliary sulfur substances. The concentration of sulfur dioxide gas generated by burning secondary sulfur species is high. For example, combustion of sulfur, if the combustion is sufficient, there is no residual O2SO in the combustion gas2The proportion of gas to the total volume of gas can reach 21%, excess air may be present in the actual combustion, and even SO, the SO produced2The volume ratio of the gas can reach 10 to 15 percent; if pyrite is burned, SO is produced2The volume ratio of the gas can reach 7 percent; the sulfur-rich active carbon (the sulfur dioxide content can reach about 70 percent generally) is formed in the desulfurization by the active carbon method, and SO is in gas generated after combustion2The content is also very high. After the high-concentration sulfur dioxide gas generated by burning the secondary sulfur substances passes through the primary absorption tower, the concentration of the sulfur dioxide in the residual gas is still very high, after the secondary absorption tower absorbs the high-concentration sulfur dioxide gas, the concentration of the discharged sulfur dioxide gas hardly meets the emission requirement, if the concentration of ammonia in the secondary absorption tower is increased, the sulfur dioxide can be completely absorbed, but ammonia escape possibly exists, and resources are wasted.
In the standard of industrial ammonium sulfite in China (HG/T2784-1996), the requirements of qualified industrial-grade solid ammonium sulfite products are that the content of ammonium sulfite is not less than 85%, the content of ammonium bisulfite is not more than 1%, and the content of ammonium sulfate is not more than 7%. The common method for producing high-purity ammonium sulfite basically takes high-grade sulfide minerals as raw materials, adopts a single process to produce the ammonium sulfite, does not consider the problems of comprehensive utilization of resources and environmental protection because of the pure pursuit of optimization of products, has limited product quantity and high cost.
Disclosure of Invention
The invention aims to provide a process and a device for producing ammonium sulfite and a byproduct thiosulfate mixed nutrient solution aiming at the defects of the prior art, and solve the problem of high cost of thiosulfate fertilizers.
The invention also aims to solve the problems of large pollution and complex process in the prior art for producing the thiosulfate mixed nutrient solution.
The invention also aims to solve the problems that sublimed sulfur is easily generated by burning sulfur and a pipeline is easily blocked after long-term operation when ammonium sulfite is produced in the prior art.
The technical scheme adopted by the invention is as follows.
The process for producing ammonium sulfite and by-producing thiosulfate mixed nutrient solution is characterized by comprising the following steps:
burning sulfur in a sulfur burning furnace to produce smoke rich in high-concentration sulfur dioxide gas; enabling the flue gas to enter a cyclone separation tower for dust removal, enabling the flue gas after dust removal to enter a heat exchanger, and reducing the temperature to 60-70 ℃; the flue gas enters a washing and purifying tower, the structure of the washing and purifying tower is similar to that of a cyclone separation tower, only an atomizing nozzle is arranged at the upper part, and atomized water is sprayed by the atomizing nozzle to wash solid matters in the flue gas; then the flue gas enters a first-stage absorption tower, the first-stage absorption tower at least comprises a spray head, a plurality of purification chambers and a bottom groove from top to bottom, a circulating pump is arranged outside the tower, the solution in the bottom groove is continuously conveyed to the spray head through a pipeline, a bottom plate of each purification chamber is provided with a plurality of small holes, atomized solution is sprayed out of the spray head, and the atomized solution is sprayed out of the spray headAmmonia and (NH)4)2SO3The method comprises the following steps of controlling the pH value of a solution to be 5-6, enabling a high-concentration ammonium bisulfite solution generated by reaction to fall into a bottom tank of a primary absorption tower, and enabling the high-concentration ammonium bisulfite solution to flow into a neutralization tank from the bottom tank after the concentration meets the requirement; then the flue gas enters a secondary absorption tower, the structure of the secondary absorption tower is the same as that of the primary absorption tower, atomized solution is sprayed out of a spray head, and the solution is composed of ammonia water and (NH)4)2SO3The composition is characterized in that the pH value of the solution is controlled to be 6-7; then the flue gas enters a three-stage absorption tower; the third absorption tower has the same structure as the first absorption tower, and is sprayed with atomized solution comprising ammonia water and (NH)4)2SO3The composition is characterized in that the pH value of the solution is controlled to be 6-7; and the flue gas discharged by the third-stage absorption tower is discharged by the tail gas absorption tower.
Measuring the concentration and volume of the bottom tank ammonium bisulfite solution of the first-stage absorption tower, and calculating the amount of ammonium bisulfite needed for neutralizing the ammonium bisulfite into a sulfurous acid solution; enabling the ammonium sulfite solution to flow into a neutralization tank, adding ammonium bicarbonate, cooling the neutralization tank by adopting a water cooling device, crystallizing saturated ammonium sulfite for a period of time, and depositing the saturated ammonium sulfite at the bottom of the neutralization tank; and a centrifugal machine is arranged at the bottom of the neutralization tank, the crystallized solid ammonium sulfite is thrown out of the neutralization tank by the centrifugal machine, and a solid ammonium sulfite product is formed after collection.
The neutralization tank is provided with a water cooling device, and the temperature of the liquid in the neutralization tank is reduced to below 10 ℃ by the water cooling device.
And (3) separating the residual solution after solid sulfurous acid is separated in the neutralization tank, introducing the residual solution into a mixed nutrient solution generation kettle, measuring the content of ammonium sulfite in the residual solution, calculating the amount of alkali and the amount of sulfur required for converting ammonium sulfite in the solution into thiosulfate, converting ammonium sulfite into alkali required by the amount of sodium thiosulfate and adding excessive sulfur powder into the mixed nutrient solution generation kettle.
The circulating water of the washing and purifying tower can enter the liquid fertilizer generating kettle.
A steam generator is adopted to cool the sulfur burning furnace, when the sulfur burning furnace burns, the temperature of the furnace body is kept at 750-800 ℃, water vapor generated by the steam generator is introduced into the mixed nutrient solution generating kettle, the temperature of liquid in the mixed nutrient solution generating kettle is slowly raised to 80-85 ℃ within 40-60 minutes, and gas generated by the mixed nutrient solution generating kettle is introduced into a primary absorption tower or a secondary absorption tower or a tertiary absorption tower;
continuously introducing the water vapor into the mixed nutrient solution generation kettle to enable the temperature of liquid in the mixed nutrient solution generation kettle to reach 90-95 ℃, preserving the temperature for a period of time, and enabling the generated gas to enter a primary absorption tower or a secondary absorption tower or a tertiary absorption tower;
the alkali is one of sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide;
when the alkali added into the mixed nutrient solution generation kettle is sodium hydroxide or potassium hydroxide, keeping positive pressure in the mixed nutrient solution generation kettle during heat preservation; when the alkali added into the mixed nutrient solution generating kettle is calcium hydroxide or magnesium hydroxide, negative pressure is kept in the mixed nutrient solution generating kettle during heat preservation.
And opening the mixed nutrient solution generation kettle, and adding acid or alkali into the solution in the mixed nutrient solution generation kettle to adjust the pH value of the mixed nutrient solution.
Filtering to generate mixed nutrient solution, and putting the filtered residue into a combustion furnace for combustion to generate flue gas rich in high-concentration sulfur dioxide gas.
As a preferred technical scheme, before the mixed nutrient solution is generated by filtration, the method also comprises the step of adding a nitrogen fertilizer and a phosphate fertilizer to adjust the fertilizer efficiency of the mixed nutrient solution.
As a preferred technical scheme, a solution generated after washing flue gas in a washing and purifying tower enters a degassing tower for degassing, the degassing tower is of an empty tower structure, and the top of the degassing tower is provided with a gas outlet; the solution after degassing enters a washing circulation tank for precipitation, and solid precipitates such as biochemical sulfur and the like which are rich in incomplete combustion are separated and then are put into a sulfur incinerator for combustion for cyclic utilization; the gas produced in the degassing tower is sent to the first-stage absorption tower.
As a preferable technical scheme, the solution participating in the reaction in the third-stage absorption tower is conveyed to the second-stage absorption tower for reaction, and the solution participating in the reaction in the second-stage absorption tower is conveyed to the first-stage absorption tower for reaction.
As a preferable technical scheme, the sulfur is sulfur-containing substances generated after coal or petroleum is desulfurized, and the sulfur content is not less than 85%.
As a preferred technical scheme, when the alkali added into the mixed nutrient solution generating kettle is sodium hydroxide or potassium hydroxide, the pressure of the mixed nutrient solution generating kettle is controlled to be 0.1-0.3MPa for 6-8 hours during heat preservation; when the alkali added into the mixed nutrient solution generating kettle is calcium hydroxide or magnesium hydroxide, the pressure of the mixed nutrient solution generating kettle is controlled between-0.02 MPa and-0.05 MPa, and the time is 10-12 hours.
As a preferred technical scheme, when the alkali added into the mixed nutrient solution generating kettle is sodium hydroxide or potassium hydroxide, the pH value of the mixed nutrient solution is controlled to be 8.3-8.6; when the alkali added into the mixed nutrient solution generating kettle is calcium hydroxide or magnesium hydroxide, the pH value of the mixed nutrient solution is controlled to be 6.5-6.9.
The device for producing ammonium sulfite and by-producing the thiosulfate mixed nutrient solution by adopting any one process comprises a sulfur incinerator, a cyclone separation tower, a heat exchanger, a washing and purifying tower, a primary absorption tower, a secondary absorption tower, a tertiary absorption tower, a tail gas absorption tower, a degassing tower, three circulating tanks, a washing circulating pool, a filter, an ammonium sulfite finished product packaging device, an ammonia water tank, a sulfur crushing tank, a steam generator, a centrifugal machine, a neutralization tank, an alkali tank and a mixed nutrient solution generating kettle;
the sulfur burning furnace is connected with the cyclone separation tower through a pipeline; the cyclone separation tower is connected with the washing and purifying tower through a pipeline, and a heat exchanger is arranged on the pipeline; the bottom of the washing and purifying tower is connected with the degassing tower through a pipeline, and the top of the washing and purifying tower is connected with the bottom of the primary absorption tower through a pipeline; the bottom of the degassing tower is connected with a washing circulation pool through a pipeline; the washing circulation tank is connected with an atomizing spray head arranged at the top end in the washing purification tower through a pipeline, and a circulation pump is arranged on the pipeline; the top of the degassing tower is connected with the bottom of the primary absorption tower through a pipeline;
the first-stage absorption tower, the second-stage absorption tower and the third-stage absorption tower have the same structure and respectively comprise a tower body, the lower part of the tower body is provided with a gas inlet, the top of the tower body is provided with a gas outlet, a spray head and a plurality of purification chambers are sequentially arranged from top to bottom between the upper part of the gas inlet and the lower part of the gas outlet, and the bottom of the tower body is provided with a bottom groove; the bottom plate of the purifying chamber is provided with a plurality of holes for gas and absorption liquid to pass through; a circulating tank is respectively arranged below the first-stage absorption tower, the second-stage absorption tower and the third-stage absorption tower; the spray heads of the first-stage absorption tower, the second-stage absorption tower and the third-stage absorption tower are respectively connected with a circulating tank below the first-stage absorption tower, the second-stage absorption tower and the third-stage absorption tower through pipelines, and circulating pumps are arranged on the pipelines; the ammonia water tank is connected with each circulating tank through a pipeline; the gas outlet of the first-stage absorption tower is connected with the gas inlet of the second-stage absorption tower through a pipeline; the gas outlet of the second-stage absorption tower is connected with the gas inlet of the third-stage absorption tower through a pipeline; the gas outlet of the third-stage absorption tower is connected with the tail gas absorption tower;
the circulating tank below the third-stage absorption tower is connected with the circulating tank below the second-stage absorption tower through a pipeline; the circulating tank below the secondary absorption tower is connected with the circulating tank below the primary absorption tower through a pipeline; the washing circulation tank is connected with the liquid fertilizer generating kettle.
The bottom groove of the primary absorption tower is connected with the neutralization tank through a pipeline; a centrifugal machine is arranged on the neutralization tank, and the ammonium sulfite finished product packaging device is connected with the centrifugal machine; the mixed nutrient solution generating kettle is connected with the neutralizing tank through a pipeline; the alkali tank is connected with the mixed nutrient solution generating kettle through a pipeline; the mixed nutrient solution generating kettle is connected with a steam generator through a pipeline, and the steam generator is connected with a sulfur burner; the sulfur crushing tank is connected with the mixed nutrient solution generating kettle through a pipeline;
the mixed nutrient solution generating kettle is connected with a gas inlet of the primary absorption tower, a gas inlet of the secondary absorption tower or a gas inlet of the tertiary absorption tower through a pipeline, and a vacuum pump and a pressure stabilizing valve are arranged on the pipeline;
the filter is connected with the mixed nutrient solution generating kettle through a pipeline.
As the preferred technical scheme, a water cooling device is arranged on the heat exchanger; a water cooling device is arranged on the neutralization tank.
According to the preferred technical scheme, a water tank is arranged below the tail gas absorption tower, a spraying device is arranged at the top end inside the tail gas absorption tower, and the bottom end of the tail gas absorption tower is connected with the water tank through a pipeline; the water tank is connected with the spraying device through a pipeline; the water tank is connected with a circulating tank below the third-stage absorption tower through a pipeline.
The invention has the following beneficial effects.
1. The problem of tail gas emission is solved. The flue gas is dedusted by the cyclone separation tower, and the gas is cooled by the cooling equipment. If the secondary sulfur substances such as sulfur and the like are not fully combusted and possibly contain certain solid impurities such as biochemical sulfur and the like, the sulfur-rich gas is washed by water through the washing and purifying tower, and the impurities such as biochemical sulfur and the like which are not fully combusted can be washed out and recovered in the washing and circulating tank. The recovered biochemical sulfur-rich solid can be combusted again. The solution generated after the washing and purifying tower is washed contains certain SO2Further degassing may be carried out in a degassing column (9) to recover SO therefrom2. SO with three absorption towers2Wherein the first-stage absorption tower is mainly used for treating high-concentration SO2Due to SO and concentration of ammonium bisulfite2The gas concentration is high, and the concentration of the ammonia water and the ammonium sulfite solution participating in the reaction is generally low (the concentration of pure ammonia water is 25% -33%), so that the purity of the generated ammonium bisulfite solution is high. Generally, in the first-stage absorption tower, the gas is continuously circulated, and the SO content in the gas is about 75 percent2Is absorbed. The second-stage absorption tower is mainly used for absorbing SO2And providing ammonium sulfite absorption liquid for the first-stage desulfurizing tower, wherein SO in the gas is2The concentration is obviously reduced, and the main component in the product is ammonium sulfite. Generally, in the secondary absorption tower, the gas is continuously circulated, and the SO content in the gas is about 75 percent2Is absorbed. The concentration of sulfur dioxide in the three-stage absorption tower is low, the concentration of ammonia in the absorption liquid is low, the residual ammonia in the reaction is little, the absorbed gas is washed by water, and SO in the gas2And the discharge amount of ammonia gas is very low, and the discharge requirement can be completely met. The desulfurizing tower is provided with a plurality of layers of purifying chambers, and solves the problems that in the prior art, gas is not fully contacted with circulating liquid, dead angles exist easily, and the desulfurizing efficiency is low.
2. The gas generated by the mixed nutrient solution generating kettle is recovered. The gas generated in the mixed nutrient solution generating kettle is mainly ammonia gas which is introduced into the first-stage absorption tower, the second-stage absorption tower or the third-stage absorption tower for continuous recycling, and the problem of great pollution in thiosulfate production in the prior art is solved.
3. Energy is saved. The mixed nutrient solution generating kettle is heated by water vapor, the energy generated by the water vapor comes from a sulfur incinerator, and meanwhile, excessive sulfur (1.02-1.05 times of the amount of the sulfur required by the reaction) is adopted, so that the energy generated by the sulfur incinerator is fully utilized, a good environment is created for the thionation reaction, and the thionation is full. The steam generator is adopted to cool the sulfur burning furnace, so that the temperature of the furnace body is kept at 750-800 ℃ when the sulfur burning furnace burns, the combustion gas of the sulfur burning furnace is ensured, and the generation of sublimed sulfur is reduced, thereby preventing the sublimed sulfur from being attached to a pipeline to block the pipeline during long-term operation, and reducing the content of impurities in the solution.
4. Solves the problem that solid thiosulfate fertilizer easily causes harm to plants in the prior art, and has lower manufacturing cost. The solid thiosulfate fertilizer solution decomposes elemental sulfur, and is directly applied to leaves or roots of plants, so that the damage to the plants is easily caused, and the equation is as follows:
the invention directly produces the thiosulfate mixed nutrient solution. The decomposition of the mixed nutrient solution containing thiosulfate is a long process, and the decomposed elemental sulfur has a good bactericidal effect. The liquid containing low-concentration thiosulfate is easy to treat, can avoid the harm to plants caused by solid thiosulfate fertilizer, and has little nitrogen component in soil dissolved out into rivers and lakes caused by nitrification.
The invention neutralizes the high-concentration ammonium bisulfite solution generated in the first-stage absorption tower by utilizing ammonium bicarbonate, and the impurity content in the separated ammonium bisulfite crystal after cooling crystallization is very low. The sulfur residue obtained by filtering sulfur residue from burning sulfur, sulfur residue desulfurized by carbon disulfide, industrial defective sulfur, sulfur residue, sulfur mud, sulfur paste, etc. can be used as raw materials of sulfur burning furnace, such as active carbon method for desulfurization to form sulfur-rich activityWaste sulfur such as charcoal, the combustion gas of which is mainly SO2And CO2The ammonium hydrogen carbonate is generated by the reaction with ammonia water, which is needed by the method for neutralizing the ammonium hydrogen sulfite solution, so that industrial-grade solid ammonium sulfite crystals with high purity can be produced by burning waste sulfur by using the method, and thiosulfate is a byproduct. The solution remained after the ammonium bisulfite solution is neutralized by the method can be further supplemented into an absorption tower to be used as a desulfurizing agent. When the concentration of the dissolved liquid ammonia in the water washing tower is higher, the dissolved liquid ammonia can also be supplemented into the three-stage absorption tower. The invention has high SO purification2And other harmful acid gases, effectively improves the utilization rate of the ammonia absorbent, and the like, can obtain high-purity solid ammonium sulfite, and has good special industrial application and prospect.
Drawings
FIG. 1 is a schematic structural diagram of a preferred embodiment of the apparatus for producing ammonium sulfite and co-producing mixed thiosulfate nutrient solution according to the present invention.
Fig. 2 is a partially enlarged view of a portion a of fig. 1.
Fig. 3 is a partially enlarged view of a portion B of fig. 1.
FIG. 4 is a schematic structural diagram of a preferred embodiment of the apparatus for producing mixed nutrient solution of ammonium sulfite and thiosulfate as byproduct according to the present invention.
Fig. 5 is a partially enlarged view of a portion C of fig. 4.
FIG. 6 is a schematic structural diagram of a preferred embodiment of the apparatus for producing mixed nutrient solution of ammonium sulfite and thiosulfate as byproduct according to the present invention.
Fig. 7 is a partially enlarged view of a portion D of fig. 6.
Wherein: a sulfur incinerator-1; a cyclone separation column-2; a heat exchanger-3; washing and purifying tower-4; a first-stage absorption tower-5; a secondary absorption tower-6; a third-stage absorption tower-7; a tail gas absorption tower-8; a degassing tower-9; a spray head-10; a clean room-11; a bottom plate-12; a bottom groove-13; a recycle tank-14; a washing circulation tank-15; a filter-16; an ammonium sulfite finished product packaging device-17; ammonia tank-18; a sulphur grinding tank-19; a steam generator-20; a centrifuge-21; neutralization tank-22; alkali tank-23; mixing the nutrient solution to generate a kettle-24; a valve-25; a circulation pump-26; a vacuum pump-27; a pressure maintaining valve-28.
Detailed Description
Example 1. As shown in fig. 1-3, the process for producing ammonium sulfite and by-producing a mixed nutrient solution of thiosulfate is characterized by comprising the following steps:
putting sulfur into a sulfur incinerator 1 for combustion to generate flue gas rich in high-concentration sulfur dioxide gas; the flue gas enters a cyclone separation tower 2 for dust removal, the flue gas after dust removal enters a heat exchanger 3, and the temperature is reduced to 60-70 ℃; the flue gas enters a washing and purifying tower 4, the structure of the washing and purifying tower 4 is similar to that of the cyclone separation tower 2, only the upper part is provided with an atomizing nozzle 41, and atomized water sprayed by the atomizing nozzle 41 washes solid matters in the flue gas; then the flue gas enters a first-stage absorption tower 5, the first-stage absorption tower 5 at least comprises a spray head 10, a plurality of purification chambers 11 and a bottom groove 13 from top to bottom, a circulating pump is arranged outside the tower, the solution in the bottom groove 13 is continuously conveyed into the spray head 10 through a pipeline, a bottom plate 12 of each purification chamber 11 is provided with a plurality of small holes, atomized solution is sprayed out of the spray head 10 and consists of ammonia water and (NH)4)2SO3The pH value of the solution is controlled to be 5-6, the high-concentration ammonium bisulfite solution generated by the reaction falls into a bottom groove 13 of a primary absorption tower 5, and flows into a neutralization tank 22 from the bottom groove 13 when the concentration meets the requirement; then the flue gas enters a secondary absorption tower 6, the structure of the secondary absorption tower 6 is the same as that of the primary absorption tower 5, and atomized solution is sprayed out by a spray head 10 and consists of ammonia water and (NH)4)2SO3The composition is characterized in that the pH value of the solution is controlled to be 6-7; then the flue gas enters a three-stage absorption tower 7; the third absorption tower 7 has the same structure as the first absorption tower 5, and the atomized solution is sprayed from the spray head 10, and the solution is composed of ammonia water and (NH)4)2SO3The composition is characterized in that the pH value of the solution is controlled to be 6-7; and the flue gas discharged from the third-stage absorption tower 7 is discharged from a tail gas absorption tower 8. A plurality of layers of grid plates are arranged in the tail gas absorption tower 8.
Measuring the concentration and volume of the ammonium bisulfite solution in the bottom tank 13 of the primary absorption tower 5, and calculating the amount of ammonium bicarbonate needed for neutralizing the ammonium bisulfite into the sulfurous acid solution; the ammonium sulfite solution flows into a neutralization tank22, adding ammonium bicarbonate, cooling the neutralization tank 22 by adopting a water cooling device, crystallizing saturated ammonium sulfite for a period of time, and depositing the saturated ammonium sulfite to the bottom of the neutralization tank 22; the bottom of the neutralization tank 22 is provided with a centrifuge 21, the crystallized solid ammonium sulfite is thrown out of the neutralization tank 22 by the centrifuge 21, and a solid ammonium sulfite product with the molecular formula of (NH) is formed after collection4)SO3·H2And O. Cyclone separation towers, also known as cyclones, are a device used for the separation of gas-solid systems or liquid-solid systems. The working principle is that solid particles or liquid drops with larger inertial centrifugal force are thrown to the outer wall surface to be separated by the rotating motion caused by tangential introduction of air flow. The cyclone separator has the main characteristics of simple structure, high operation flexibility, high efficiency, convenient management and maintenance and low price, is used for collecting dust with the diameter of more than 5-10 mu m, is widely applied to the pharmaceutical industry, is particularly suitable for being used as an internal separation device of a fluidized bed reactor or a pre-separator under the conditions of coarse dust particles, high dust concentration and high temperature and high pressure, and is separation equipment with wide industrial application.
The neutralization tank is provided with a water cooling device, and the temperature of the liquid in the neutralization tank is reduced to below 10 ℃ by the water cooling device.
The content of ammonium sulfite in the residual solution after solid sulfurous acid separation in the neutralization tank 22 is usually about 20%, the solution is introduced into the mixed nutrient solution generation kettle 24, the content of ammonium sulfite in the residual solution is measured, the amount of alkali and the amount of sulfur required for converting the ammonium sulfite in the solution into thiosulfate are calculated, and the alkali required for converting the ammonium sulfite into the sodium thiosulfate and the excessive sulfur powder are added into the mixed nutrient solution generation kettle 24.
The steam generator 20 is adopted to cool the sulfur burner 1, so that when the sulfur burner 1 is burnt, the temperature of a furnace body is kept at 750 ℃, steam generated by the steam generator 20 is introduced into the mixed nutrient solution generating kettle 24, the temperature of liquid in the mixed nutrient solution generating kettle 24 is slowly raised to 80 ℃ within 40 minutes, and gas generated by the mixed nutrient solution generating kettle 24 is introduced into the primary absorption tower 5.
Continuously introducing the water vapor into the mixed nutrient solution generation kettle 24 to ensure that the temperature of the liquid in the mixed nutrient solution generation kettle 24 is between 90 and 95 ℃, preserving the heat for a period of time, and introducing the generated gas into the primary absorption tower 5, the secondary absorption tower 6 or the tertiary absorption tower 7; the pressure of the mixed nutrient solution generating kettle is kept at 0.1MPa for 4 hours.
The mixed nutrient solution generating kettle 24 is opened, and acid or alkali is added into the solution in the mixed nutrient solution generating kettle to adjust the pH value of the mixed nutrient solution.
Filtering to generate mixed nutrient solution, and putting the filtered residue into a combustion furnace for combustion to generate flue gas rich in high-concentration sulfur dioxide gas.
The invention is based on the basic principle of ammonia desulphurization and is improved on the basis of the prior ammonia desulphurization. In order to obtain SO of high purity2The gas, in the combustion chamber, burns high purity sulphur, the chemical reaction formula of which is:
S+O2→SO2 (1) 。
through dust removal, dust in the gas is further clarified, and after the gas is washed by the washing and purifying tower, the biochemical sulfur which is not fully combusted in the flue gas is cleaned, SO that SO in the flue gas is further improved2The purity of the gas.
The principle of ammonia desulfurization is to use ammonia water with a certain concentration and SO in flue gas2Reaction to obtain desulfurization and production (NH)4)2SO3The purpose of (1). The reaction equation is as follows:
2NH3+SO2+H2O→(NH4)2SO3 (2)；
(NH4)2SO3+SO2+H2O→2NH4HSO3 (3)；
NH4HSO3+NH3→(NH4)2SO3 (4)。
the alkali added to the mixed nutrient solution generating kettle 24 is sodium hydroxide.
(NH4)2SO3(4) +2NaOH→Na2SO3+2NH3+2H2O (5)。
Na2SO3+S→Na2S2SO3 (6)。
Before filtering to generate the mixed nutrient solution, the method also comprises the step of adding a nitrogen fertilizer and a phosphate fertilizer to adjust the fertilizer efficiency of the mixed nutrient solution.
The solution generated after washing the flue gas in the washing and purifying tower 4 enters a degassing tower 9 for degassing, the degassing tower 9 is of an empty tower structure, and the top of the degassing tower is provided with a gas outlet; the solution after degassing enters a washing circulation pool 15 for precipitation, and solid precipitates such as biochemical sulfur and the like which are rich in incomplete combustion are separated and then are put into a sulfur incinerator 1 for combustion for recycling; the gas produced in the degassing tower 9 is sent to the primary absorption tower 5. The circulating water of the washing and purifying tower can enter the liquid fertilizer generating kettle.
The solution in the third absorption tower 7 is sent to the second absorption tower 6 for reaction, and the solution in the second absorption tower 6 is sent to the first absorption tower 5 for reaction.
The sulfur is sulfur-containing substances generated after coal or petroleum desulfurization, and the sulfur content is not less than 85%. Can be black sulfur of a coking plant, secondary sulfur of a chemical fertilizer plant, sulfur filtration sulfur slag of a sulfuric acid plant, sulfur slag desulfurized by carbon disulfide, industrial defective sulfur, sulfur slag, sulfur mud, sulfur paste and the like.
The pH value of the mixed nutrient solution is controlled to be 6.5.
The device for producing ammonium sulfite and by-producing the thiosulfate mixed nutrient solution comprises a sulfur incinerator 1, a cyclone separation tower 2, a heat exchanger 3, a washing and purifying tower 4, a primary absorption tower 5, a secondary absorption tower 6, a tertiary absorption tower 7, a tail gas absorption tower 8, a degassing tower 9, three circulating tanks 14, a washing circulating pool 15, a filter 16, an ammonium sulfite finished product packaging device 17, an ammonia water tank 18, a sulfur crushing tank 19, a steam generator 20, a centrifuge 21, a neutralization tank 22, an alkali tank 23 and a mixed nutrient solution generating kettle 24.
The sulfur incinerator 1 is connected with the cyclone separation tower 2 through a pipeline; the cyclone separation tower 2 is connected with a washing and purifying tower 4 through a pipeline, and a heat exchanger 3 is arranged on the pipeline; the bottom of the washing and purifying tower 4 is connected with the degassing tower 9 through a pipeline, and the top of the washing and purifying tower 4 is connected with the bottom of the primary absorption tower 5 through a pipeline; the bottom of the degassing tower 9 is connected with a washing circulation pool 15 through a pipeline; the washing circulation tank 15 is connected with an atomizing spray nozzle 41 arranged at the top end in the washing and purifying tower 4 through a pipeline, and a circulation pump is arranged on the pipeline; the top of the degassing tower 9 is connected to the bottom of the primary absorption tower 5 through a pipeline.
The primary absorption tower 5, the secondary absorption tower 6 and the tertiary absorption tower 7 have the same structure and respectively comprise a tower body, the lower part of the tower body is provided with a gas inlet, the top of the tower body is provided with a gas outlet, a spray head 10 and a plurality of purification chambers 11 are sequentially arranged from top to bottom between the upper part of the gas inlet and the lower part of the gas outlet, and the bottom of the tower body is provided with a bottom groove 13; a bottom plate 12 of the purifying chamber 11 is provided with a plurality of holes for allowing gas and absorption liquid to pass through; a circulating tank 14 is respectively arranged below the first-stage absorption tower 5, the second-stage absorption tower 6 and the third-stage absorption tower 7; the spray heads 10 of the first-stage absorption tower 5, the second-stage absorption tower 6 and the third-stage absorption tower 7 are respectively connected with a circulating tank 14 below the first-stage absorption tower, and a circulating pump is arranged on the pipeline; the ammonia tank 18 is connected with each circulation tank 14 through a pipeline; the gas outlet of the primary absorption tower 5 is connected with the gas inlet of the secondary absorption tower 6 through a pipeline; the gas outlet of the second-stage absorption tower 6 is connected with the gas inlet of the third-stage absorption tower 7 through a pipeline; a gas outlet of the third-stage absorption tower 7 is connected with a tail gas absorption tower 8; the tail gas absorption tower structure 8 is the same as the washing and purifying tower structure.
The circulating tank 14 below the third-stage absorption tower 7 is connected with the circulating tank 14 below the second-stage absorption tower 6 through a pipeline; the circulation tank 14 below the secondary absorption tower 6 is connected with the circulation tank 14 below the primary absorption tower 5 through a pipeline. The washing circulation tank 15 is connected to a liquid fertilizer production tank 24. A valve 26 is arranged on a pipeline between the washing circulation tank 15 and the liquid fertilizer generating kettle 24. A circulating pump 25 is arranged on a pipeline between the washing circulating pool 15 and the liquid fertilizer generating kettle 24.
The bottom groove 13 of the primary absorption tower 5 is connected with a neutralization tank 22 through a pipeline; a centrifuge 21 is arranged on the neutralization tank 22, and the ammonium sulfite finished product packaging device 17 is connected with the centrifuge 21; the mixed nutrient solution generating kettle 24 is connected with the neutralization tank 22 through a pipeline; the alkali tank 23 is connected with the mixed nutrient solution generating kettle 24 through a pipeline; the mixed nutrient solution generating kettle 24 is connected with a steam generator 20 through a pipeline, the steam generator 20 is connected with the sulfur burner 1, and the steam generator 20 obtains energy from the sulfur burner 1; the sulfur crushing tank 19 is connected with the mixed nutrient solution generating kettle 24 through a pipeline;
the mixed nutrient solution generating kettle 24 is connected with a gas inlet of the primary absorption tower 5 through a pipeline; the pipeline is provided with a vacuum pump 27 and a pressure stabilizing valve 28.
The filter 16 is connected to the mixed nutrient solution generating tank 24 through a pipe. A water cooling device is arranged on the heat exchanger 3; the neutralization tank 22 is provided with a water cooling device.
A water tank 81 is arranged below the tail gas absorption tower 8, a spraying device 82 is arranged at the top end inside the tail gas absorption tower 8, and the bottom end of the tail gas absorption tower 8 is connected with the water tank 81 through a pipeline; the water tank 81 is connected with the spraying device 82 through a pipeline; the water tank 81 is connected to the circulation tank 14 below the tertiary absorption tower 7 through a pipe.
Brief introduction of the experiment: during the experiment, the flue gas is simulated flue gas consisting of mixed gas, the experimental flow is the same as that in the figure 1, but the flow starts from a first-stage absorption tower, and the simulated flue gas enters the flow after being preheated to 60 ℃. Test example 1. Simulating the smoke composition: 78% of N 23% of O 215% SO23% of CO2And water vapor. Flue gas flow rate: 1m3And/min. Circulating ammonia water and (NH) in the first-stage absorption tower4)2SO3The pH value of the solution is 5-6; circulating ammonia water and (NH) in secondary absorption tower4)2SO3The pH value of the solution is 6-7; circulating ammonia water and (NH) in three-stage absorption tower4)2SO3The pH value of the solution is 6-7. And (3) test results: flue gas flow rate 1 (m)3Min), purified SO2Content 57 (ppm), NH after purification3Content 31 (ppm), impurity content 5% in solid ammonium sulfite. The produced mixed nutrient solution is colorless and transparent, and the impurity content is less than 0.5 percent.
Test example 2. Simulating the smoke composition: 78% of N 24% of O 210% SO27% of CO2And steam. Flue gas flow rate: 1m3And/min. Circulating ammonia water and (NH) in the first-stage absorption tower4)2SO3The pH value of the solution is 5-6; circulating ammonia water and (NH) in secondary absorption tower4)2SO3The pH value of the solution is 6-7; circulating ammonia water and (NH) in three-stage absorption tower4)2SO3The pH value of the solution is 6-7. And (3) test results: flue gas flow rate 1 (m)3Min), purified SO2Content 65 (ppm), NH after purification3Content 28 (ppm), impurity content 4% in solid ammonium sulfite. The produced mixed nutrient solution is colorless and transparent, and the impurity content is less than 0.5 percent.
Test example 3: the simulated smoke composition is as follows: 78% of N 28% of O 27% SO25% of CO2And water vapor. Flue gas flow rate: 1m3And/min. Circulating ammonia water and (NH) in the first-stage absorption tower4)2SO3The pH value of the solution is 6-7; circulating ammonia water and (NH) in secondary absorption tower4)2SO3The pH value of the solution is 6-7; circulating ammonia water and (NH) in three-stage absorption tower4)2SO3The pH value of the solution is 6-7. And (3) test results: flue gas flow rate 1 (m)3Min), purified SO2Content 58(ppm), NH after purification3The content is 62(ppm), and the impurity content in solid ammonium sulfite is 5 percent. The produced mixed nutrient solution is colorless and transparent, and the impurity content is less than 0.5 percent.
Test example 4: the simulated smoke composition is as follows: 78% of N 23% of O2% of 10% SO28% of CO2And water vapor. Flue gas flow rate: 1m3And/min. Circulating ammonia water and (NH) in the first-stage absorption tower4)2SO3The pH value of the solution is 5-6; circulating ammonia water and (NH) in secondary absorption tower4)2SO3The pH value of the solution is 6-7; circulating ammonia water and (NH) in three-stage absorption tower4)2SO3The pH value of the solution is 6-7. And (3) test results: flue gas flow rate 1 (m)3Min), purified SO2Content 62(ppm), NH after purification3Content 27 (ppm)) And the impurity content in the solid ammonium sulfite is 5 percent. The produced mixed nutrient solution is colorless and transparent, and the impurity content is less than 0.5 percent.
The beneficial effects of the present embodiment are as follows.
1. The problem of tail gas emission is solved. The flue gas is dedusted by the cyclone separation tower 2, and the gas is cooled by cooling equipment. If the secondary sulfur substances such as sulfur and the like are not fully combusted and may contain certain solid impurities such as biochemical sulfur and the like, the sulfur-rich gas is washed by the washing and purifying tower 4, and the impurities such as biochemical sulfur and the like which are not fully combusted can be washed out and recovered in the washing and circulating tank 15. The recovered biochemical sulfur-rich solid can be combusted again. The solution generated after the washing and purifying tower is washed contains certain SO2Further degassing may be carried out in a degassing column 9 to recover SO therefrom2. SO with three absorption towers2Wherein the first-stage absorption tower is mainly used for treating high-concentration SO2Due to SO and concentration of ammonium bisulfite2The gas concentration is very high, and the concentration of the ammonia water and the ammonium sulfite solution which participate in the reaction is generally 25 to 33 percent of that of the lower pure ammonia water, so that the purity of the generated ammonium bisulfite solution is very high. Generally, in the first-stage absorption tower, the gas is continuously circulated, and the SO content in the gas is about 75 percent2Is absorbed. The second-stage absorption tower is mainly used for absorbing SO2And providing ammonium sulfite absorption liquid for the first-stage desulfurizing tower, wherein SO in the gas is2The concentration is obviously reduced, and the main component in the product is ammonium sulfite. Generally, in the secondary absorption tower, the gas is continuously circulated, and the SO content in the gas is about 75 percent2Is absorbed. The concentration of sulfur dioxide in the three-stage absorption tower is low, the concentration of ammonia in the absorption liquid is low, the residual ammonia in the reaction is little, the absorbed gas is washed by water, and SO in the gas2And the discharge amount of ammonia gas is very low, and the discharge requirement can be completely met. The desulfurizing tower is provided with a plurality of layers of purifying chambers, and solves the problems that in the prior art, gas is not fully contacted with circulating liquid, dead angles exist easily, and the desulfurizing efficiency is low.
2. The gas generated in the mixed nutrient solution generating tank 24 is recovered. The gas generated in the mixed nutrient solution generating kettle 24 is mainly ammonia gas which is introduced into the first-stage absorption tower 5, the second-stage absorption tower 6 or the third-stage absorption tower 7 for continuous recycling, and the problem of great pollution in thiosulfate production in the prior art is solved.
3. Energy is saved. The mixed nutrient solution generating kettle 24 is heated by water vapor, the energy generated by the water vapor comes from the sulfur incinerator 1, meanwhile, the excessive sulfur reaction is adopted, the amount of the sulfur is 1.02-1.05 times of the amount of the sulfur, the energy generated by the sulfur incinerator 1 is fully utilized, a good environment is created for the sulfur reaction, and the sulfur is fully reacted. The steam generator 20 is adopted to cool the sulfur incinerator 1, so that when the sulfur incinerator 1 burns, the furnace body temperature is kept at 750-800 ℃, the combustion gas of the sulfur incinerator 1 is ensured, the generation of sublimed sulfur is reduced, the sublimed sulfur is prevented from being attached to a pipeline to block the pipeline during long-term operation, and the content of impurities in the solution is also reduced.
4. Solves the problem that solid thiosulfate fertilizer easily causes harm to plants in the prior art, and has lower manufacturing cost. The solid thiosulfate fertilizer solution decomposes elemental sulfur, and is directly applied to leaves or roots of plants, so that the damage to the plants is easily caused, and the equation is as follows:
the invention directly produces the thiosulfate mixed nutrient solution. The decomposition of the mixed nutrient solution containing thiosulfate is a long process, and the decomposed elemental sulfur has a good bactericidal effect. The liquid containing low-concentration thiosulfate is easy to treat, can avoid the harm to plants caused by solid thiosulfate fertilizer, and has little nitrogen component in soil dissolved out into rivers and lakes caused by nitrification.
The circulating liquid in the washing circulating pool 15 can enter the liquid fertilizer generating kettle 24, and finally the pH value is adjusted to be well utilized.
The invention neutralizes the high-concentration ammonium bisulfite solution generated in the first-stage absorption tower by using ammonium bicarbonate, and the impurity content in the separated ammonium sulfite crystal is also reduced after temperature crystallizationIs very low. The sulfur slag filtered by burning sulfur, the sulfur slag desulfurized by carbon disulfide, industrial defective sulfur, sulfur slag, sulfur mud, sulfur paste and the like can be used as raw materials of the sulfur burning furnace 1, for example, waste sulfur such as activated carbon rich in sulfur is formed in the desulfurization by an activated carbon method, and the generated gas of combustion is mainly SO2And CO2The ammonium hydrogen carbonate is generated by the reaction with ammonia water, which is needed by the method for neutralizing the ammonium hydrogen sulfite solution, so that industrial-grade solid ammonium sulfite crystals, namely ammonium sulfite monohydrate, with high purity can be produced by burning waste sulfur by using the method, and simultaneously thiosulfate is a byproduct. The solution remained after the ammonium bisulfite solution is neutralized by the method can be further supplemented into an absorption tower to be used as a desulfurizing agent. When the concentration of the dissolved liquid ammonia in the water washing tower is higher, the dissolved liquid ammonia can also be supplemented into the three-stage absorption tower. The invention has high SO purification2And other harmful acid gases, effectively improves the utilization rate of the ammonia absorbent, and the like, can obtain high-purity solid ammonium sulfite, and has good special industrial application and prospect.
Example 2. As shown in fig. 4 to 5, the present embodiment is different from embodiment 1 in that: the liquid fertilizer generating kettle 24 is connected with a gas inlet of the secondary absorption tower 6 through a pipeline, and a vacuum pump 27 and a pressure stabilizing valve 28 are arranged on the pipeline; a steam generator is adopted to cool the sulfur burner, when the sulfur burner is burnt, the temperature of a furnace body is kept at 800 ℃, steam generated by the steam generator is introduced into a mixed nutrient solution generating kettle, the temperature of liquid in the mixed nutrient solution generating kettle is slowly raised to 85 ℃ within 60 minutes, and gas generated by the mixed nutrient solution generating kettle is introduced into a secondary absorption tower; and continuously introducing the water vapor into the mixed nutrient solution generation kettle to ensure that the temperature of the liquid in the mixed nutrient solution generation kettle reaches 90 ℃, preserving the heat for a period of time, and introducing the generated gas into a secondary absorption tower. The mixed nutrient solution produces alkaline calcium hydroxide in kettle 24. The mixed nutrient solution generating kettle keeps negative pressure and the pressure is not more than 0.3MPa, and the time is 12 hours. The pH value of the mixed nutrient solution is controlled to be 6.9.
The chemical reaction is as follows: (NH)4)2SO3(4) +2KOH→K2SO3+2NH3+2H2O (7)。
K2SO3+S→K2S2SO3 (8)。
Example 3. As shown in fig. 6 to 7, the present embodiment is different from embodiment 1 in that: the liquid fertilizer generating kettle 24 is connected with a gas inlet of the three-stage absorption tower 7 through a pipeline, and a vacuum pump 27 and a pressure stabilizing valve 28 are arranged on the pipeline; the alkali in the mixed nutrient solution generating kettle 24 is potassium hydroxide. A steam generator is adopted to cool the sulfur burner, when the sulfur burner is burnt, the temperature of a furnace body is kept at 760 ℃, steam generated by the steam generator is introduced into a mixed nutrient solution generating kettle, the temperature of liquid in the mixed nutrient solution generating kettle is slowly raised to 82 ℃ within 50 minutes, and gas generated by the mixed nutrient solution generating kettle is introduced into a three-stage absorption tower; continuously introducing the water vapor into the mixed nutrient solution generation kettle to ensure that the temperature of the liquid in the mixed nutrient solution generation kettle is 95 ℃, preserving the heat for 6 hours, and introducing the generated gas into a three-stage absorption tower; the pressure of the mixed nutrient solution generating kettle is controlled at-0.02 MPa during heat preservation. The pH value of the mixed nutrient solution is controlled to be 8.6.
The chemical reaction is as follows: (NH)4)2SO3(4) +Ca(OH)2→CaSO3+2NH3+2H2O (9)。
CaSO3+S→CaS2SO3 (10)。
The pH value of the mixed nutrient solution is controlled at 6.5 by adding a potassium hydroxide solution.
Example 4. This embodiment is different from embodiment 1 in that: the alkali in the mixed nutrient solution generating kettle 24 is magnesium hydroxide. A steam generator is adopted to cool the sulfur burning furnace, so that when the sulfur burning furnace burns, the temperature of a furnace body is kept at 800 ℃, steam generated by the steam generator is introduced into a mixed nutrient solution generating kettle, and the temperature of liquid in the mixed nutrient solution generating kettle is slowly raised to 80 ℃ within 60 minutes; and continuously introducing the water vapor into the mixed nutrient solution generation kettle to ensure that the temperature of the liquid in the mixed nutrient solution generation kettle is 92 ℃, and preserving the temperature for 10 hours. The negative pressure of the mixed nutrient solution generating kettle is kept and the pressure is not more than-0.05 MPa, and the pH value of the mixed nutrient solution is controlled at 6.9.
The chemical reaction is as follows: (NH)4)2SO3(4) +Mg(OH)2→CaSO3+2NH3+2H2O (11)。
Mg SO3+S→MgS2SO3 (12)。
The above-mentioned embodiments are only for understanding the present invention, and are not intended to limit the technical solutions of the present invention, and those skilled in the art can make various changes or modifications based on the technical solutions described in the claims, and all equivalent changes or modifications should be covered by the scope of the claims of the present invention. The present invention is not described in detail, but is known to those skilled in the art.
Claims (10)
1. The process for producing ammonium sulfite and by-producing thiosulfate mixed nutrient solution is characterized by comprising the following steps:
burning sulfur in a sulfur burning furnace to produce smoke rich in high-concentration sulfur dioxide gas; enabling the flue gas to enter a cyclone separation tower for dust removal, enabling the flue gas after dust removal to enter a heat exchanger, and reducing the temperature to 60-70 ℃; the flue gas enters a washing and purifying tower, the structure of the washing and purifying tower is similar to that of a cyclone separation tower, only an atomizing nozzle is arranged at the upper part, and atomized water is sprayed by the atomizing nozzle to wash solid matters in the flue gas; then the flue gas enters a first-stage absorption tower, the first-stage absorption tower at least comprises a spray head, a plurality of purification chambers and a bottom groove from top to bottom, a circulating pump is arranged outside the tower, the solution in the bottom groove is continuously conveyed to the spray head through a pipeline, the bottom plate of each purification chamber is provided with a plurality of small holes, atomized solution is sprayed out of the spray head, and the solution is composed of ammonia water and (NH)4)2SO3The method comprises the following steps of controlling the pH value of a solution to be 5-6, enabling a high-concentration ammonium bisulfite solution generated by reaction to fall into a bottom tank of a primary absorption tower, and enabling the high-concentration ammonium bisulfite solution to flow into a neutralization tank from the bottom tank after the concentration meets the requirement; then the flue gas enters a secondary absorption tower, the structure of the secondary absorption tower is the same as that of the primary absorption tower, atomized solution is sprayed out of a spray head, and the solution is composed of ammonia water and (NH)4)2SO3The composition is characterized in that the pH value of the solution is controlled to be 6-7; then the flue gas enters a three-stage absorption tower; the third absorption tower has the same structure as the first absorption tower, and is sprayed with atomized solution comprising ammonia water and (NH)4)2SO3The composition is characterized in that the pH value of the solution is controlled to be 6-7; the flue gas discharged by the third-stage absorption tower is discharged by a tail gas absorption tower;
measuring the concentration and volume of the bottom tank ammonium bisulfite solution of the first-stage absorption tower, and calculating the amount of ammonium bisulfite needed for neutralizing the ammonium bisulfite into a sulfurous acid solution; enabling the ammonium sulfite solution to flow into a neutralization tank, adding ammonium bicarbonate, cooling the neutralization tank by adopting a water cooling device, crystallizing saturated ammonium sulfite for a period of time, and depositing the saturated ammonium sulfite at the bottom of the neutralization tank; a centrifugal machine is arranged at the bottom of the neutralization tank, the crystallized solid ammonium sulfite is thrown out of the neutralization tank by the centrifugal machine, and a solid ammonium sulfite product is formed after collection;
the neutralization tank is provided with a water cooling device, and the temperature of the liquid in the neutralization tank is reduced to below 10 ℃ by the water cooling device;
the residual solution obtained after solid sulfurous acid is separated in the neutralization tank is introduced into a mixed nutrient solution generation kettle, the content of ammonium sulfite in the residual solution is measured, the amount of alkali and the amount of sulfur required for converting ammonium sulfite in the solution into thiosulfate are calculated, and the alkali required for converting the ammonium sulfite into sodium thiosulfate and excessive sulfur powder are added into the mixed nutrient solution generation kettle;
circulating water of the washing and purifying tower can enter the liquid fertilizer generation kettle;
a steam generator is adopted to cool the sulfur burning furnace, when the sulfur burning furnace burns, the temperature of the furnace body is kept at 750-800 ℃, water vapor generated by the steam generator is introduced into the mixed nutrient solution generating kettle, the temperature of liquid in the mixed nutrient solution generating kettle is slowly raised to 80-85 ℃ within 40-60 minutes, and gas generated by the mixed nutrient solution generating kettle is introduced into a primary absorption tower or a secondary absorption tower or a tertiary absorption tower;
continuously introducing the water vapor into the mixed nutrient solution generation kettle to enable the temperature of liquid in the mixed nutrient solution generation kettle to reach 90-95 ℃, preserving the temperature for a period of time, and enabling the generated gas to enter a primary absorption tower or a secondary absorption tower or a tertiary absorption tower;
the alkali is one of sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide;
when the alkali added into the mixed nutrient solution generation kettle is sodium hydroxide or potassium hydroxide, keeping positive pressure in the mixed nutrient solution generation kettle during heat preservation;
when the alkali added into the mixed nutrient solution generating kettle is calcium hydroxide or magnesium hydroxide, keeping negative pressure in the mixed nutrient solution generating kettle during heat preservation;
opening the mixed nutrient solution generation kettle, and adding acid or alkali into the solution in the mixed nutrient solution generation kettle to adjust the pH value of the mixed nutrient solution;
filtering to generate mixed nutrient solution, and putting the filtered residue into a combustion furnace for combustion to generate flue gas rich in high-concentration sulfur dioxide gas.
2. The process for producing ammonium sulfite and by-producing a thiosulfate mixed nutrient solution according to claim 1, characterized in that: before filtering to generate the mixed nutrient solution, the method also comprises the step of adding a nitrogen fertilizer and a phosphate fertilizer to adjust the fertilizer efficiency of the mixed nutrient solution.
3. The process for producing ammonium sulfite and by-producing a thiosulfate mixed nutrient solution according to claim 1, characterized in that: the solution generated after washing the flue gas in the washing and purifying tower enters a degassing tower for degassing, the degassing tower is of an empty tower structure, and the top of the degassing tower is provided with a gas outlet; the solution after degassing enters a washing circulation tank for precipitation, and solid precipitates such as biochemical sulfur and the like which are rich in incomplete combustion are separated and then are put into a sulfur incinerator for combustion for cyclic utilization; the gas produced in the degassing tower is sent to the first-stage absorption tower.
4. The process for producing ammonium sulfite and by-producing a thiosulfate mixed nutrient solution according to claim 1, characterized in that: and conveying the solution participating in the reaction in the third absorption tower to the second absorption tower for reaction, and conveying the solution participating in the reaction in the second absorption tower to the first absorption tower for reaction.
5. The process for producing ammonium sulfite and by-producing thiosulfate mixed nutrient solution according to claim 1, which is characterized in that: the sulfur is sulfur-containing substances generated after coal or petroleum desulfurization, and the sulfur content is not less than 85%.
6. The process for producing ammonium sulfite and by-producing a thiosulfate mixed nutrient solution according to claim 1, characterized in that:
when the alkali added into the mixed nutrient solution generating kettle is sodium hydroxide or potassium hydroxide, the pressure of the mixed nutrient solution generating kettle is controlled to be 0.1-0.3MPa for 6-8 hours during heat preservation; when the alkali added into the mixed nutrient solution generating kettle is calcium hydroxide or magnesium hydroxide, the pressure of the mixed nutrient solution generating kettle is controlled between-0.02 MPa and-0.05 MPa, and the time is 10-12 hours.
7. The process for producing ammonium sulfite and by-producing a thiosulfate mixed nutrient solution according to claim 1, characterized in that: when the alkali added into the mixed nutrient solution generating kettle is sodium hydroxide or potassium hydroxide, the pH value of the mixed nutrient solution is controlled to be 8.3-8.6; when the alkali added into the mixed nutrient solution generating kettle is calcium hydroxide or magnesium hydroxide, the pH value of the mixed nutrient solution is controlled to be 6.5-6.9.
8. The device for producing ammonium sulfite and by-producing thiosulfate mixed nutrient solution by adopting the process of any one of claims 1 to 7 is characterized in that: the device comprises a sulfur incinerator, a cyclone separation tower, a heat exchanger, a washing and purifying tower, a primary absorption tower, a secondary absorption tower, a tertiary absorption tower, a tail gas absorption tower, a degassing tower, three circulating tanks, a washing circulating pool, a filter, an ammonium sulfite finished product packaging device, an ammonia water tank, a sulfur crushing tank, a steam generator, a centrifuge, a neutralization tank, an alkali tank and a mixed nutrient solution generating kettle;
the sulfur burning furnace is connected with the cyclone separation tower through a pipeline; the cyclone separation tower is connected with the washing and purifying tower through a pipeline, and a heat exchanger is arranged on the pipeline; the bottom of the washing and purifying tower is connected with the degassing tower through a pipeline, and the top of the washing and purifying tower is connected with the bottom of the primary absorption tower through a pipeline; the bottom of the degassing tower is connected with a washing circulation pool through a pipeline; the washing circulation tank is connected with an atomizing spray head arranged at the top end in the washing purification tower through a pipeline, and a circulation pump is arranged on the pipeline; the top of the degassing tower is connected with the bottom of the primary absorption tower through a pipeline;
the first-stage absorption tower, the second-stage absorption tower and the third-stage absorption tower have the same structure and respectively comprise a tower body, the lower part of the tower body is provided with a gas inlet, the top of the tower body is provided with a gas outlet, a spray head and a plurality of purification chambers are sequentially arranged from top to bottom between the upper part of the gas inlet and the lower part of the gas outlet, and the bottom of the tower body is provided with a bottom groove; the bottom plate of the purifying chamber is provided with a plurality of holes for gas and absorption liquid to pass through; a circulating tank is respectively arranged below the first-stage absorption tower, the second-stage absorption tower and the third-stage absorption tower; the spray heads of the first-stage absorption tower, the second-stage absorption tower and the third-stage absorption tower are respectively connected with a circulating tank below the first-stage absorption tower, the second-stage absorption tower and the third-stage absorption tower through pipelines, and circulating pumps are arranged on the pipelines; the ammonia water tank is connected with each circulating tank through a pipeline; the gas outlet of the first-stage absorption tower is connected with the gas inlet of the second-stage absorption tower through a pipeline; the gas outlet of the second-stage absorption tower is connected with the gas inlet of the third-stage absorption tower through a pipeline; the gas outlet of the third-stage absorption tower is connected with the tail gas absorption tower;
the circulating tank below the third-stage absorption tower is connected with the circulating tank below the second-stage absorption tower through a pipeline; the circulating tank below the secondary absorption tower is connected with the circulating tank below the primary absorption tower through a pipeline;
the washing circulation tank is connected with the liquid fertilizer generation kettle;
the bottom groove of the primary absorption tower is connected with the neutralization tank through a pipeline; a centrifugal machine is arranged on the neutralization tank, and the ammonium sulfite finished product packaging device is connected with the centrifugal machine; the mixed nutrient solution generating kettle is connected with the neutralizing tank through a pipeline; the alkali tank is connected with the mixed nutrient solution generating kettle through a pipeline; the mixed nutrient solution generating kettle is connected with a steam generator through a pipeline, and the steam generator is connected with a sulfur burner; the sulfur crushing tank is connected with the mixed nutrient solution generating kettle through a pipeline;
the mixed nutrient solution generating kettle is connected with a gas inlet of the primary absorption tower, a gas inlet of the secondary absorption tower or a gas inlet of the tertiary absorption tower through a pipeline, and a vacuum pump and a pressure stabilizing valve are arranged on the pipeline;
the filter is connected with the mixed nutrient solution generating kettle through a pipeline.
9. The apparatus according to claim 8, wherein the apparatus comprises: a water cooling device is arranged on the heat exchanger; a water cooling device is arranged on the neutralization tank.
10. The apparatus according to claim 8, wherein the apparatus comprises: a water tank is arranged below the tail gas absorption tower, a spraying device is arranged at the top end inside the tail gas absorption tower, and the bottom end of the tail gas absorption tower is connected with the water tank through a pipeline; the water tank is connected with the spraying device through a pipeline; the water tank is connected with a circulating tank below the third-stage absorption tower through a pipeline.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110364172.7A CN112973411A (en) | 2021-04-04 | 2021-04-04 | Process and device for producing ammonium sulfite and byproduct thiosulfate mixed nutrient solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110364172.7A CN112973411A (en) | 2021-04-04 | 2021-04-04 | Process and device for producing ammonium sulfite and byproduct thiosulfate mixed nutrient solution |
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| CN202110364172.7A Pending CN112973411A (en) | 2021-04-04 | 2021-04-04 | Process and device for producing ammonium sulfite and byproduct thiosulfate mixed nutrient solution |
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