CN112973412A - Process and device for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer - Google Patents
Process and device for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer Download PDFInfo
- Publication number
- CN112973412A CN112973412A CN202110364173.1A CN202110364173A CN112973412A CN 112973412 A CN112973412 A CN 112973412A CN 202110364173 A CN202110364173 A CN 202110364173A CN 112973412 A CN112973412 A CN 112973412A
- Authority
- CN
- China
- Prior art keywords
- tower
- absorption tower
- liquid fertilizer
- sulfur
- pipeline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 205
- 239000003337 fertilizer Substances 0.000 title claims abstract description 171
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 50
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims abstract description 29
- 238000010521 absorption reaction Methods 0.000 claims abstract description 218
- 239000007789 gas Substances 0.000 claims abstract description 166
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 162
- 239000011593 sulfur Substances 0.000 claims abstract description 143
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 143
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 141
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000003546 flue gas Substances 0.000 claims abstract description 65
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000005406 washing Methods 0.000 claims abstract description 60
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 55
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 42
- 239000007787 solid Substances 0.000 claims abstract description 40
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 238000002485 combustion reaction Methods 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 12
- 239000000428 dust Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 42
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 42
- 238000007872 degassing Methods 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 31
- 239000007921 spray Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 26
- 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 23
- 239000000047 product Substances 0.000 claims description 23
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 22
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 22
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 22
- 239000001099 ammonium carbonate Substances 0.000 claims description 22
- 238000000746 purification Methods 0.000 claims description 22
- 238000006477 desulfuration reaction Methods 0.000 claims description 16
- 230000023556 desulfurization Effects 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 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
- 239000006227 byproduct Substances 0.000 abstract description 9
- 238000007280 thionation reaction Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 92
- 238000004519 manufacturing process Methods 0.000 description 23
- 239000012535 impurity Substances 0.000 description 17
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 16
- 235000019345 sodium thiosulphate Nutrition 0.000 description 16
- 239000002893 slag Substances 0.000 description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 14
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000003009 desulfurizing effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 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
- 239000000779 smoke Substances 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
- 230000036760 body temperature Effects 0.000 description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 4
- 230000002950 deficient Effects 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
- 239000005864 Sulphur Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000567 combustion gas Substances 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
- 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
- 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
- 229910052799 carbon 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
- 238000002156 mixing Methods 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
- 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
- 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
- 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
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 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
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- 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
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
-
- 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
- B01D53/73—After-treatment of removed components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/79—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/50—Inorganic acids
- B01D2251/512—Phosphoric acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/608—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Treating Waste Gases (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a process and a device for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer, wherein the process comprises the steps of putting waste sulfur into a sulfur incinerator for combustion to generate flue gas rich in high-concentration sulfur dioxide gas; the flue gas enters a cyclone separation tower for dust removal, the flue gas after dust removal enters a heat exchanger and a washing and purifying tower for treatment, and then enters a primary absorption tower, a secondary absorption tower and a tertiary absorption tower for absorption, and the flue gas is discharged through a sulfur dioxide removal tower and an ammonia removal tower. And (3) separating solid ammonium sulfite from the liquid in the first-stage absorption tower, the second-stage absorption tower and the third-stage absorption tower in a neutralization tank, carrying out a thionation reaction on the residual liquid and circulating liquid of the washing and purifying tower, the sulfur dioxide removing tower and the ammonia removing tower in a liquid fertilizer generation kettle, and finally adjusting the pH value of the liquid in the liquid fertilizer generation kettle by using alkali to obtain the liquid fertilizer. The method can obtain high-purity solid ammonium sulfite and byproduct ammonium thiosulfate fertilizer, and has good special industrial application and prospect.
Description
Technical Field
The invention relates to a liquid fertilizer production process and a device, in particular to a process and a device for producing ammonium sulfite and ammonium thiosulfate liquid fertilizer.
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, the equipment volume is small, and no secondary is generatedAnd in addition, a desulfurization byproduct, namely 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
An object of the present invention is to provide a process and an apparatus for producing ammonium sulfite and byproduct ammonium thiosulfate liquid fertilizer, which solves the problem of high cost of thiosulfate fertilizer.
The invention also aims to solve the problems of large pollution and complex process in the prior art for producing the ammonium thiosulfate liquid fertilizer.
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 ammonium thiosulfate liquid fertilizer is characterized by comprising the following steps:
putting the waste sulfur into a sulfur incinerator for combustion to generate flue gas 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 third-stage absorption tower, the structure of the third-stage absorption tower is the same as that of the first-stage 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; the flue gas discharged from the third-stage absorption tower is treated by a tail gas sulfur dioxide removal tower and a tail gas ammonia removal tower and then discharged; the sulfur dioxide removing tower sprays low-concentration alkali liquor to clean the flue gas, and the tail gas ammonia removing tower sprays low-concentration acid liquor to clean the flue gas.
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 controlled 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 liquid fertilizer generation kettle, the ammonium sulfite content of the residual solution is measured, the ammonium quantity and the sulfur quantity required for converting ammonium sulfite in the solution into ammonium thiosulfate are calculated, the required ammonium bicarbonate quantity is converted according to the required ammonium quantity and the concentration of low-concentration ammonia water, and the ammonium sulfite is converted into the ammonia water, the ammonium bicarbonate and excessive sulfur powder which are required for converting the ammonium sulfite into the ammonium thiosulfate and added into the liquid fertilizer generation kettle;
the circulating liquid of the washing purification tower, the sulfur dioxide removal tower and the ammonia removal tower can enter the liquid fertilizer generation kettle.
The 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 ℃, the steam generated by the steam generator is introduced into the liquid fertilizer generation kettle, so that the temperature of the liquid in the liquid fertilizer generation kettle is slowly raised to 50-65 ℃ within 40-60 minutes, and the gas generated by the liquid fertilizer generation kettle is introduced into the primary absorption tower or the secondary absorption tower or the tertiary absorption tower.
Continuously introducing the water vapor into the liquid fertilizer generation kettle to ensure that the liquid temperature in the liquid fertilizer generation kettle reaches 100-105 ℃, keeping the pressure of the liquid fertilizer generation kettle at 0.1-0.3MPa, and preserving the heat for 2-4 hours, and introducing the gas in the liquid fertilizer generation kettle into the primary absorption tower or the secondary absorption tower or the tertiary absorption tower when the pressure exceeds the pressure range;
opening the liquid fertilizer generation kettle, and adjusting the pH value of liquid in the liquid fertilizer generation kettle to 8.3-8.6 by using alkali;
filtering to generate liquid fertilizer, 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, the method also comprises the step of adding a nitrogen fertilizer and a phosphate fertilizer to adjust the fertilizer efficiency of the liquid fertilizer before filtering to generate the liquid fertilizer.
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 an optimal technical scheme, the low-concentration alkali liquor sprayed by the sulfur dioxide removal tower and the low-concentration acid liquor sprayed by the tail gas ammonia removal tower are added into the liquid fertilizer generation kettle when the tail gas is absorbed and the pH value is 6-8.
As a preferred technical scheme, the alkali is potassium hydroxide; the acid is sulfuric acid or phosphoric acid.
Adopt the device of any one above-mentioned technology production ammonium sulfite and by-product ammonium thiosulfate liquid fertilizer, its 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 sulfur dioxide removal tower, a tail gas ammonia removal tower, a degassing tower, three circulating tanks, a washing circulating pool, a filter, an ammonium sulfite finished product packaging device, an ammonia water tank, sulfur crushing, a steam generator, a centrifugal machine, a neutralization tank, an ammonium bicarbonate tank and a liquid fertilizer generation 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 first-stage 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 secondary absorption tower is connected with a tail gas sulfur dioxide removal tower; the tail gas sulfur dioxide removal tower is connected with the tail gas ammonia removal 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 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 liquid fertilizer generating kettle is connected with the neutralizing tank through a pipeline; the ammonium bicarbonate groove is respectively connected with the liquid fertilizer generating kettle and the neutralizing tank through pipelines.
The ammonia water tank is connected with the liquid fertilizer generation kettle through a pipeline, and a valve is arranged on the pipeline.
The liquid fertilizer generating kettle is connected with a steam generator through a pipeline, and the steam generator is connected with a sulfur burner; the sulfur crushing is connected with a liquid fertilizer generating kettle through a pipeline; the liquid fertilizer generating kettle is connected with a gas inlet of the first-stage absorption tower, a gas inlet of the second-stage absorption tower or a gas inlet of the third-stage absorption tower through a pipeline; the filter is connected with the liquid fertilizer generating kettle through a pipeline.
The washing and purifying tower is connected with the liquid fertilizer generating kettle through a pipeline.
The steam generator is arranged on the outer wall of the sulfur burner.
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 low-concentration alkali liquor tank is arranged below the tail gas sulfur dioxide removal tower, a low-concentration alkali liquor spraying device is arranged at the top end inside the tail gas sulfur dioxide removal tower, and the bottom end of the tail gas sulfur dioxide removal tower is connected with the low-concentration alkali liquor tank through a pipeline; the low-concentration alkali liquor tank is connected with a low-concentration alkali liquor spraying device through a pipeline; the low-concentration lye tank is connected with the liquid fertilizer generating kettle through a pipeline;
a low-concentration acid liquid tank is arranged below the tail gas ammonia removal tower, a low-concentration acid liquid spraying device is arranged at the top end inside the tail gas ammonia removal tower, and the bottom end of the tail gas ammonia removal tower is connected with the low-concentration acid liquid tank through a pipeline; the low-concentration acid liquid tank is connected with a low-concentration acid liquid spraying device through a pipeline; the low-concentration acid liquid tank is connected with the liquid fertilizer generation kettle through a pipeline.
The beneficial effects of the invention are as follows.
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 washing and purification, and the impurities such as biochemical sulfur and the like which are not fully combusted can be washed out and recovered in a washing circulation 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 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 problem of the prior desulfurizing towerIn the technology, the gas is not fully contacted with the circulating liquid, so that dead corners easily exist and the desulfurization efficiency is low.
2. The gas generated by the liquid fertilizer generating kettle is recovered. The gas generated in the liquid fertilizer generation 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 high pollution in ammonium thiosulfate production in the prior art is solved.
3. Energy is saved. The liquid fertilizer generating kettle is heated by water vapor, the energy generated by the water vapor comes from the sulfur incinerator, and meanwhile, the 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 the solid ammonium 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 ammonium thiosulfate liquid fertilizer. The decomposition of liquid fertilizers containing thiosulphate is a long process, and the decomposed elemental sulphur 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 cools the ammonium bisulfite solutionThe ammonium sulfite crystals separated after crystallization also have a very low impurity content. 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, for example, waste sulfur such as activated carbon rich in sulfur is formed in desulfurization by an activated carbon method, and the gas generated by burning 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 simultaneously ammonium 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 ammonium thiosulfate liquid fertilizer of 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 ammonium sulfite and ammonium thiosulfate liquid fertilizer of the present invention.
Fig. 5 is a partially enlarged view of a portion C of fig. 4.
Fig. 6 is a partially enlarged view of a portion D of fig. 4.
FIG. 7 is a schematic structural diagram of a preferred embodiment of the apparatus for producing ammonium sulfite and ammonium thiosulfate liquid fertilizer of the present invention.
Fig. 8 is a partially enlarged view of a portion E of fig. 7.
Fig. 9 is a partially enlarged view of a portion F of fig. 7.
Fig. 10 is a partially enlarged view of a portion G of fig. 7.
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 sulfur dioxide removal tower-8; low concentration lye tank-81; a tail gas ammonia removal tower-82; a low-concentration alkali liquor spraying device-83; a low-concentration acid liquor spraying device-84; a low-concentration acid solution tank-85; 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; ammonium bicarbonate tank-23; liquid fertilizer generating kettle-24; a valve-25; a circulation pump-26.
Detailed Description
Example 1. As shown in fig. 1-3, the process for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer is characterized by comprising the following steps:
putting the waste 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 heat exchanger 3 is cooled by water. 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 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 suctionA tower 5 is collected, the inside of the first-stage absorption tower 5 at least comprises a spray head 12, 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 12 through a pipeline, a bottom plate 12 of the purification chambers 11 is provided with a plurality of small holes, atomized solution is sprayed out of the spray head 12, and the solution is composed 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 when the concentration meets the requirement, the high-concentration ammonium bisulfite solution flows into a neutralization tank 22 from the bottom groove 13.
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 12 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 third-stage absorption tower 7, the structure of the third-stage absorption tower 7 is the same as that of the first-stage absorption tower 5, and atomized solution is sprayed out by a spray head 12 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.
The flue gas discharged from the third-stage absorption tower 7 is discharged after being treated by a tail gas sulfur dioxide removal tower 8 and a tail gas ammonia removal tower 82; the sulfur dioxide removal tower 8 sprays low-concentration alkali liquor to clean the flue gas, and the tail gas ammonia removal tower 82 sprays low-concentration acid liquor to clean the flue gas. A plurality of layers of grids with meshes are respectively arranged in the sulfur dioxide removing tower 8 and the tail gas ammonia removing tower 82.
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; enabling the ammonium sulfite solution to flow into a neutralization tank 22, 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 at the bottom of the neutralization tank 22; a centrifuge 21 is arranged at the bottom of the neutralization tank 22, the crystallized solid ammonium sulfite is thrown out of the neutralization tank 22 by the centrifuge 21, and a solid ammonium sulfite product is formed after collection; the molecular formula is (NH)4)SO3·H2O。
And (3) introducing the residual solution obtained after the solid sulfurous acid is separated in the neutralization tank 22 into the liquid fertilizer generation kettle 24, measuring the ammonium sulfite content of the residual solution, calculating the ammonium quantity and the sulfur quantity required for converting ammonium sulfite in the solution into ammonium thiosulfate, converting the required ammonium bicarbonate quantity according to the required ammonium quantity and the concentration of low-concentration ammonia water, and converting the ammonium sulfite into the ammonia water, the ammonium bicarbonate and excessive sulfur powder required for converting the ammonium sulfite into the ammonium thiosulfate and adding the ammonia water, the ammonium bicarbonate and the excessive sulfur powder into the liquid fertilizer generation kettle 24.
The neutralization tank is provided with a water cooling device, and the temperature of the liquid in the neutralization tank is controlled below 10 ℃ by the water cooling device.
The circulating liquid of the washing purification tower, the sulfur dioxide removal tower and the ammonia removal tower can enter the liquid fertilizer generation kettle.
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 water vapor generated by the steam generator 20 is introduced into the liquid fertilizer generation kettle 24, the liquid temperature in the liquid fertilizer generation kettle 24 is slowly raised to 50 ℃ within 40 minutes, and the gas generated by the liquid fertilizer generation kettle 24 is introduced into the primary absorption tower 5 or the secondary absorption tower 6 or the tertiary absorption tower 7.
Continuously introducing the water vapor into the liquid fertilizer generation kettle 24 to ensure that the temperature of the liquid in the liquid fertilizer generation kettle 24 is 100 ℃, keeping the pressure of the liquid fertilizer generation kettle 24 at 0.1MPa and preserving the heat for 2 hours, and introducing the gas in the liquid fertilizer generation kettle 24 into the primary absorption tower 5 or the secondary absorption tower 6 or the tertiary absorption tower 7 when the pressure exceeds the pressure range; after the completion, the gas in the liquid fertilizer production kettle 24 is introduced into the primary absorption tower 5.
Opening the liquid fertilizer generation kettle 24, and adjusting the pH value of the liquid in the liquid fertilizer generation kettle 24 to 8.3 by using alkali; filtering to generate liquid fertilizer, and putting the filtered residue into a combustion furnace for combustion to generate flue gas rich in high-concentration sulfur dioxide gas.
Before the liquid fertilizer 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 liquid fertilizer.
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 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 low-concentration alkali liquor sprayed by the sulfur dioxide removal tower 8 and the low-concentration acid liquor sprayed by the tail gas ammonia removal tower 82 are added into the liquid fertilizer generation kettle 24 when the tail gas is absorbed and the pH value is 6-8.
The alkali is potassium hydroxide; the acid is phosphoric acid.
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:
S+O2→SO2 (1) 。
2NH3+SO2+H2O→(NH4)2SO3 (2)。
(NH4)2SO3+SO2+H2O→2NH4HSO3 (3)。
NH4HSO3+NH3→(NH4)2SO3 (4)。
the alkali added into the liquid fertilizer generating kettle (24) is sodium hydroxide.
(NH4)2SO3(4) +2NaOH→Na2SO3+2NH3+2H2O (5)。
Na2SO3+S→Na2S2SO3 (6)。
The device for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer by adopting the process 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 sulfur dioxide removing tower 8, a tail gas ammonia removing tower 82, 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, sulfur crushing 19, a steam generator 20, a centrifugal machine 21, a neutralization tank 22, an ammonium bicarbonate tank 23 and a liquid fertilizer generation 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 with the bottom of the first-stage 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 12 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 12 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; the gas outlet of the secondary absorption tower 6 is connected with a tail gas sulfur dioxide removing tower 8; the tail gas sulfur dioxide removal tower 8 is connected with a tail gas ammonia removal tower 82;
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 circulating tank 14 below the secondary absorption tower 6 is connected with the circulating tank 14 below the primary absorption tower 5 through a pipeline;
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 liquid fertilizer generation kettle 24 is connected with the neutralization tank 22 through a pipeline; the ammonium bicarbonate groove 23 is respectively connected with the liquid fertilizer generating kettle 24 and the neutralizing tank 22 through pipelines;
the ammonia water tank 18 is connected with the liquid fertilizer generation kettle 24 through a pipeline, and a valve is arranged on the pipeline;
the liquid fertilizer generating kettle 24 is connected with a steam generator 20 through a pipeline, and the steam generator 20 is connected with the sulfur burner 1; the sulfur crushing 19 is connected with a liquid fertilizer generating kettle 24 through a pipeline; the liquid fertilizer generation kettle 24 is connected with a gas inlet of the primary absorption tower 5 through a pipeline; the filter 16 is connected to the liquid fertilizer production tank 24 through a pipe. The washing and purifying tower 15 is connected with the liquid fertilizer production kettle 24 through a pipeline. The steam generator 20 is installed on the outer wall of the sulfur burner 1.
A water cooling device is arranged on the heat exchanger 3; the neutralization tank 22 is provided with a water cooling device.
A low-concentration alkali liquor tank 81 is arranged below the tail gas sulfur dioxide removing tower 8, a low-concentration alkali liquor spraying device 83 is arranged at the top end inside the tail gas sulfur dioxide removing tower 8, and the bottom end of the tail gas sulfur dioxide removing tower 8 is connected with the low-concentration alkali liquor tank 81 through a pipeline; the low-concentration alkali liquor tank 81 is connected with a low-concentration alkali liquor spraying device 83 through a pipeline; the low-concentration lye tank 81 is connected with the liquid fertilizer generation kettle 24 through a pipeline;
a low-concentration acid liquid tank 85 is arranged below the tail gas ammonia removal tower 82, a low-concentration acid liquid spraying device 84 is arranged at the top end inside the tail gas ammonia removal tower 82, and the bottom end of the tail gas ammonia removal tower 82 is connected with the low-concentration acid liquid tank 85 through a pipeline; the low-concentration acid liquid tank 85 is connected with the low-concentration acid liquid spraying device 84 through a pipeline; the low-concentration acid solution tank 85 is connected to the liquid fertilizer production tank 24 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 26 (ppm), NH after purification3The content is 12 (ppm), and the impurity content in solid ammonium sulfite is 4.8 percent. The produced liquid fertilizer 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 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 32(ppm), NH after purification3The content is 11(ppm), and the impurity content in solid ammonium sulfite is 3.9 percent. The produced liquid fertilizer 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 18(ppm), NH after purification3The content is 21 (ppm), and the impurity content in solid ammonium sulfite is 4.9 percent. The produced liquid fertilizer 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 30(ppm), NH after purification3The content is 16 (ppm), and the impurity content in solid ammonium sulfite is 4.8 percent. The produced liquid fertilizer 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. By three absorptionsTower for SO2Wherein 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 in the liquid fertilizer production tank 24 is recovered. The gas generated in the liquid fertilizer generation kettle 24 is mainly ammonia gas which is introduced into the primary absorption tower 5 for continuous recycling, and the problem of large pollution in ammonium thiosulfate production in the prior art is solved.
3. Energy is saved. The liquid fertilizer generating kettle 24 is heated by water vapor, the energy generated by the water vapor comes from the sulfur incinerator 1, and meanwhile, the 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 1 is fully utilized, a good environment is created for the thionation reaction, and the thionation is full. 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 the solid ammonium 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 can directly produce the ammonium thiosulfate liquid fertilizer. The decomposition of liquid fertilizers containing thiosulphate is a long process, and the decomposed elemental sulphur 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.
5. The tail gas treatment is cleaner. The main components of the tail gas are sulfur dioxide and ammonia gas, and the sulfur dioxide removing tower 8 and the tail gas ammonia removing tower 82 can respectively remove the sulfur dioxide and the ammonia gas. The circulating liquid of the washing circulating pool 15, the sulfur dioxide removing tower 8 and the tail gas ammonia removing tower 82 can enter the liquid fertilizer generating kettle 24, and finally the pH value is adjusted to be well utilized, and no waste water is discharged in the whole process.
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 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 with high purity can be produced by burning waste sulfur by using the method, and simultaneously ammonium thiosulfate is a byproduct. The method neutralizes the ammonium bisulfite solution and the residual solutionThe liquid can be further supplemented into an absorption tower to be used as a desulfurizer. 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 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 800 ℃, steam generated by the steam generator 20 is introduced into the liquid fertilizer generation kettle 24, the liquid temperature in the liquid fertilizer generation kettle 24 is slowly raised to 65 ℃ within 60 minutes, and gas generated by the liquid fertilizer generation kettle 24 is introduced into the primary absorption tower 5 or the secondary absorption tower 6 or the tertiary absorption tower 7. Continuously introducing the water vapor into the liquid fertilizer generation kettle 24 to ensure that the temperature of the liquid in the liquid fertilizer generation kettle 24 is 105 ℃, keeping the pressure of the liquid fertilizer generation kettle 24 at 0.3MPa and preserving the heat for 4 hours, and introducing the gas in the liquid fertilizer generation kettle 24 into the primary absorption tower 5 or the secondary absorption tower 6 or the tertiary absorption tower 7 when the pressure exceeds the pressure range; after the end, the gas in the liquid fertilizer production kettle 24 is introduced into the secondary absorption tower 6. The liquid fertilizer production vessel 24 was opened, and the pH of the liquid in the liquid fertilizer production vessel 24 was adjusted to 8.3 with an alkali.
Example 3. As shown in fig. 6 to 10, the present embodiment is different from embodiment 1 in that: 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 maintained at 780 ℃, steam generated by the steam generator 20 is introduced into the liquid fertilizer generation kettle 24, the liquid temperature in the liquid fertilizer generation kettle 24 is slowly raised to 65 ℃ within 60 minutes, and gas generated by the liquid fertilizer generation kettle 24 is introduced into the primary absorption tower 5 or the secondary absorption tower 6 or the tertiary absorption tower 7. Continuously introducing the water vapor into the liquid fertilizer generation kettle 24 to ensure that the temperature of the liquid in the liquid fertilizer generation kettle 24 is 105 ℃, keeping the pressure of the liquid fertilizer generation kettle 24 at 0.3MPa and preserving the heat for 3 hours, and introducing the gas in the liquid fertilizer generation kettle 24 into the three-stage absorption tower 7 when the pressure exceeds the pressure range; after the end, the gas in the liquid fertilizer production kettle 24 is introduced into the secondary absorption tower 6. The liquid fertilizer production vessel 24 was opened, and the pH of the liquid in the liquid fertilizer production vessel 24 was adjusted to 8.5 with alkali.
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 ammonium thiosulfate liquid fertilizer is characterized by comprising the following steps:
putting the waste sulfur into a sulfur incinerator for combustion to generate flue gas 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 third-stage absorption tower, the structure of the third-stage absorption tower is the same as that of the first-stage absorption tower, and the atomized flue gas is sprayed out by a spray headA solution of ammonia 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 from the third-stage absorption tower is treated by a tail gas sulfur dioxide removal tower and a tail gas ammonia removal tower and then discharged; spraying low-concentration alkali liquor to clean the flue gas by a sulfur dioxide removal tower, and spraying low-concentration acid liquor to clean the flue gas by a tail gas ammonia removal 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;
a water cooling device is arranged on the neutralization tank, and the temperature of the liquid in the neutralization tank is controlled to be below 10 ℃ through the water cooling device;
the residual solution obtained after solid sulfurous acid is separated in the neutralization tank is introduced into a liquid fertilizer generation kettle, the ammonium sulfite content of the residual solution is measured, the ammonium quantity and the sulfur quantity required for converting ammonium sulfite in the solution into ammonium thiosulfate are calculated, the required ammonium bicarbonate quantity is converted according to the required ammonium quantity and the concentration of low-concentration ammonia water, and the ammonium sulfite is converted into the ammonia water, the ammonium bicarbonate and excessive sulfur powder which are required for converting the ammonium sulfite into the ammonium thiosulfate and added into the liquid fertilizer generation kettle;
circulating liquid of the washing purification tower, the sulfur dioxide removal tower and the ammonia removal 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 ℃, steam generated by the steam generator is introduced into a liquid fertilizer generation kettle, the temperature of liquid in the liquid fertilizer generation kettle is slowly raised to 50-65 ℃ within 40-60 minutes, and gas generated by the liquid fertilizer generation 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 liquid fertilizer generation kettle to ensure that the liquid temperature in the liquid fertilizer generation kettle reaches 100-105 ℃, keeping the pressure of the liquid fertilizer generation kettle at 0.1-0.3MPa, and preserving the heat for 2-4 hours, and introducing the gas in the liquid fertilizer generation kettle into the primary absorption tower or the secondary absorption tower or the tertiary absorption tower when the pressure exceeds the pressure range;
opening the liquid fertilizer generation kettle, and adjusting the pH value of liquid in the liquid fertilizer generation kettle to 8.3-8.6 by using alkali;
filtering to generate liquid fertilizer, 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 ammonium thiosulfate liquid fertilizer as claimed in claim 1, characterized in that: before the liquid fertilizer 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 liquid fertilizer.
3. The process for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer as claimed in 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 ammonium thiosulfate liquid fertilizer as claimed in 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 ammonium thiosulfate liquid fertilizer as claimed in claim 1, 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 ammonium thiosulfate liquid fertilizer as claimed in claim 1, characterized in that: and adding the low-concentration alkali liquor sprayed by the sulfur dioxide removal tower and the low-concentration acid liquor sprayed by the tail gas ammonia removal tower into the liquid fertilizer generation kettle when the tail gas is absorbed and the pH value is 6-8.
7. The process for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer as claimed in claim 1, characterized in that: the alkali is potassium hydroxide; the acid is sulfuric acid or phosphoric acid.
8. An apparatus for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer by the process according to any one of claims 1 to 7, 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 sulfur dioxide removal tower, a tail gas ammonia removal tower, a degassing tower, three circulating tanks, a washing circulating pool, a filter, an ammonium sulfite finished product packaging device, an ammonia water tank, sulfur crushing, a steam generator, a centrifuge, a neutralization tank, an ammonium bicarbonate tank and a liquid fertilizer generation 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 secondary absorption tower is connected with a tail gas sulfur dioxide removal tower; the tail gas sulfur dioxide removal tower is connected with the tail gas ammonia removal 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 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 liquid fertilizer generating kettle is connected with the neutralizing tank through a pipeline; the ammonium bicarbonate groove is respectively connected with the liquid fertilizer generating kettle and the neutralizing tank through pipelines;
the ammonia water tank is connected with the liquid fertilizer generation kettle through a pipeline, and a valve is arranged on the pipeline;
the liquid fertilizer generating kettle is connected with a steam generator through a pipeline, and the steam generator is connected with a sulfur burner; the sulfur crushing is connected with a liquid fertilizer generating kettle through a pipeline; the liquid fertilizer generating kettle is connected with a gas inlet of the first-stage absorption tower, a gas inlet of the second-stage absorption tower or a gas inlet of the third-stage absorption tower through a pipeline; the filter is connected with the liquid fertilizer generating kettle through a pipeline;
the washing and purifying tower is connected with the liquid fertilizer generating kettle through a pipeline;
the steam generator is arranged on the outer wall of the sulfur burner.
9. The apparatus for producing ammonium sulfite and co-producing ammonium thiosulfate liquid fertilizer according to claim 8, characterized in that: a water cooling device is arranged on the heat exchanger; a water cooling device is arranged on the neutralization tank.
10. The apparatus for producing ammonium sulfite and co-producing ammonium thiosulfate liquid fertilizer according to claim 8, characterized in that: a low-concentration alkali liquor tank is arranged below the tail gas sulfur dioxide removal tower, a low-concentration alkali liquor spraying device is arranged at the top end inside the tail gas sulfur dioxide removal tower, and the bottom end of the tail gas sulfur dioxide removal tower is connected with the low-concentration alkali liquor tank through a pipeline; the low-concentration alkali liquor tank is connected with a low-concentration alkali liquor spraying device through a pipeline; the low-concentration lye tank is connected with the liquid fertilizer generating kettle through a pipeline;
a low-concentration acid liquid tank is arranged below the tail gas ammonia removal tower, a low-concentration acid liquid spraying device is arranged at the top end inside the tail gas ammonia removal tower, and the bottom end of the tail gas ammonia removal tower is connected with the low-concentration acid liquid tank through a pipeline; the low-concentration acid liquid tank is connected with a low-concentration acid liquid spraying device through a pipeline; the low-concentration acid liquid tank is connected with the liquid fertilizer generation kettle through a pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110364173.1A CN112973412A (en) | 2021-04-04 | 2021-04-04 | Process and device for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110364173.1A CN112973412A (en) | 2021-04-04 | 2021-04-04 | Process and device for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112973412A true CN112973412A (en) | 2021-06-18 |
Family
ID=76339161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110364173.1A Pending CN112973412A (en) | 2021-04-04 | 2021-04-04 | Process and device for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112973412A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114159941A (en) * | 2021-11-29 | 2022-03-11 | 启东亚太药业有限公司 | Method and equipment for synthesizing ammonium bisulfite |
| CN115032330A (en) * | 2021-12-28 | 2022-09-09 | 大连亚泰科技新材料股份有限公司 | Testing machine for testing desulfurization effect of desulfurizing agent |
-
2021
- 2021-04-04 CN CN202110364173.1A patent/CN112973412A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114159941A (en) * | 2021-11-29 | 2022-03-11 | 启东亚太药业有限公司 | Method and equipment for synthesizing ammonium bisulfite |
| CN115032330A (en) * | 2021-12-28 | 2022-09-09 | 大连亚泰科技新材料股份有限公司 | Testing machine for testing desulfurization effect of desulfurizing agent |
| CN115032330B (en) * | 2021-12-28 | 2023-08-04 | 大连亚泰科技新材料股份有限公司 | Desulfurizing agent desulfurization effect detection testing machine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2682402C (en) | Process and apparatus for carbon capture and elimination of multi-pollutants in flue gas from hydrocarbon fuel sources and recovery of multiple by-products | |
| CN106430116B (en) | A method of the sulphur-bearing waste solution extracting sulfuric acid generated using coal gas wet oxidation method | |
| CN111701419B (en) | Sodium-alkali dry-method desulfurized fly ash recycling method | |
| CN105036438B (en) | A kind of sodium alkali desulfurization waste liquid method for innocent treatment | |
| CN112973412A (en) | Process and device for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer | |
| CN103429313A (en) | Process for removing contaminants from gas streams | |
| CN102658016B (en) | Method for ammonia method desulfurization of flue gas and high-purity ammonium hydrogen sulfite by-producing | |
| CN205653162U (en) | System for sulphuric acid is prepared to sulphur waste liquid that contains that utilizes coal gas wet oxidation process to produce | |
| DE2253806C3 (en) | Process for converting the hydrogen sulfide contained in gas mixtures with sulfur dioxide according to the Claus process | |
| CN114620692A (en) | Process for preparing sulfuric acid by carrying out salt extraction and co-firing on coking desulfurization foam sulfur melting and desulfurization waste liquid melting method | |
| CN103288286A (en) | Catalytic oxidation treatment method for desulfurized waste liquid | |
| CN112973410A (en) | Process and device for producing ammonium sulfite and by-producing ammonium thiosulfate mixed nutrient solution | |
| CN112973409A (en) | Process and device for producing ammonium sulfite and by-producing thiosulfate liquid fertilizer | |
| CN215138505U (en) | Device for producing ammonium sulfite and by-producing ammonium thiosulfate liquid fertilizer | |
| CN215138504U (en) | Device for producing ammonium sulfite and by-producing thiosulfate mixed nutrient solution | |
| CN215276588U (en) | Device for producing ammonium sulfite and by-producing thiosulfate liquid fertilizer | |
| CN215233230U (en) | Device for producing ammonium sulfite and by-producing ammonium thiosulfate mixed nutrient solution | |
| CN105731497B (en) | A kind of utilization sour gas produces the method and device of sodium acid carbonate | |
| CN101757843B (en) | Improved process for performing ammonium sulfite pulping by using sulfur-containing flue gas absorber | |
| CN112973411A (en) | Process and device for producing ammonium sulfite and byproduct thiosulfate mixed nutrient solution | |
| CN109110859A (en) | A kind of coking desulfurization waste liquor advanced treatment process | |
| CN105727714A (en) | Process and device for production of sodium hydrosulfide | |
| CN112717653B (en) | Energy-saving environment-friendly ammonia desulphurization zero-emission system and method for sulfur recovery device | |
| CN105731501B (en) | A kind of utilization sour gas produces the method and device of solid sodium bicarbonate | |
| CN104212496B (en) | Desulfurization purifier and its application method for coke-stove gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210618 |