CN212315566U - Sodium sulfate recovery plant - Google Patents
Sodium sulfate recovery plant Download PDFInfo
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- CN212315566U CN212315566U CN201920741030.6U CN201920741030U CN212315566U CN 212315566 U CN212315566 U CN 212315566U CN 201920741030 U CN201920741030 U CN 201920741030U CN 212315566 U CN212315566 U CN 212315566U
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- China
- Prior art keywords
- sodium sulfate
- mother liquor
- sodium
- reactor
- recovery apparatus
- Prior art date
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 174
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 133
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 124
- 238000011084 recovery Methods 0.000 title claims abstract description 51
- 239000012452 mother liquor Substances 0.000 claims abstract description 102
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 57
- 238000000926 separation method Methods 0.000 claims abstract description 52
- 238000010926 purge Methods 0.000 claims abstract description 50
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 47
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- 238000004064 recycling Methods 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 31
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 26
- 239000011780 sodium chloride Substances 0.000 claims abstract description 24
- 230000020477 pH reduction Effects 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005119 centrifugation Methods 0.000 claims abstract description 5
- 238000010908 decantation Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 28
- 239000003546 flue gas Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 235000017550 sodium carbonate Nutrition 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 14
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
- 229910001385 heavy metal Inorganic materials 0.000 claims description 13
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 13
- 239000002594 sorbent Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 239000007900 aqueous suspension Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 150000004763 sulfides Chemical class 0.000 claims description 9
- 239000000571 coke Substances 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 241001625808 Trona Species 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 159000000007 calcium salts Chemical class 0.000 claims description 7
- 150000004679 hydroxides Chemical class 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- -1 sulfide compound Chemical class 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 235000011132 calcium sulphate Nutrition 0.000 claims description 6
- 229910052729 chemical element Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000011669 selenium Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 238000004939 coking Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical group [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical group [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000003 Lead carbonate Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 3
- 229910000316 alkaline earth metal phosphate Inorganic materials 0.000 claims description 3
- 230000003113 alkalizing effect Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000001175 calcium sulphate Substances 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 3
- 239000010452 phosphate Substances 0.000 claims 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 241000196324 Embryophyta Species 0.000 description 26
- 239000007832 Na2SO4 Substances 0.000 description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 229910052815 sulfur oxide Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000002198 insoluble material Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000006351 Leucophyllum frutescens Species 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 159000000014 iron salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 101100020663 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) ppm-1 gene Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002916 wood waste Substances 0.000 description 1
Images
Classifications
-
- 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
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
Abstract
An apparatus for recovering sodium sulfate from a sodium sulfate waste, the sodium sulfate waste comprising sodium carbonate and optionally sodium chloride, the recovery apparatus comprising: (a) a dissolver (A) for dissolving sodium sulfate residues; (b) a separation means (B) for separating insoluble substances by filtration, decantation or centrifugation; (c1) an acidification reactor (C1) for acidifying the second aqueous solution with sulfuric acid to a pH of less than 6 in order to convert sodium carbonate to sodium sulfate; (c3) basifying the reactor (C3) to a pH of about 7 or higher; (d) an evaporator-crystallizer (D) to obtain a mother liquor and to crystallize sodium sulfate particles; (e) separating means (E) for separating sodium sulfate particles from the mother liquor; (f) purging means (F) within the evaporator-crystallizer (D) or within the separation device (E) for purging at least a portion of the mother liquor; and (G) recycling means (G) for recycling at least a portion of the mother liquor not purged in at least one of the devices (a) to (D); characterized in that the purge means (F) provides a purge weight ratio of purged separated mother liquor to un-purged separated mother liquor of at least 0.005t/t and at most 0.20 t/t.
Description
Technical Field
The present invention relates to an apparatus for recovering sodium sulfate from sodium sulfate waste, which contains sodium sulfate, sodium carbonate or bicarbonate, and insoluble matter. Many processes produce flue gases containing sulfur oxides and other organics. Most of the flue gases are produced by the combustion of carbonaceous products such as: coal, coke, oil, or organic materials such as wood or agricultural waste, paper waste, municipal and industrial waste. Most of those flue gases also contain heavy metals, especially those that are volatilized at high temperature combustion (e.g., above 800 ℃ or above 1100 ℃).
In particular the steel industry, including coke and sintering plants, also produces flue gases which, before being released into the atmosphere, are treated in order to reduce the emission of acid gases, in particular SOx (such as SO)2Or SO3) Abatement, but also organic abatement (such as aromatics, impure benzene, dioxins and furans), as well as small amounts of HX halide (such as HCl, HF, HBr, HI) and NOx abatement. This is important to reduce the risk to the health and natural protection of nearby living population.
Most SOx abatement is done worldwide using calcium alkaline compounds (such as limestone or lime) or using sodium compounds (such as sodium hydroxide, sodium bicarbonate and trona).
The use of sodium basic compounds is one of those that are rapidly developing because it is very effective. In particular, Dry Sorbent Injection (DSI) using trona or sodium bicarbonate is an interesting way to abate acid gases because it produces less vapor clouds and drier gases when released into the atmosphere compared to wet abatement methods, and less residual byproducts compared to calcium basic compounds.
For DSI with sodium-based compounds, trona or sodium bicarbonate is typically injected directly into the flue gas at a temperature above 100 ℃, and preferably above 140 ℃, either alone or with a co-sorbent such as activated carbon or lignite coke. Under hot flue gases, trona or sodium bicarbonate is converted into highly specific sodium porous carbonate particles, which react rapidly with acid gases. The salt produced, such as sodium Sulfate (SO), is then recovered on an electrostatic filter or preferably on a bag filter2And SO3Emission reduction) or sodium chloride (HCl emission reduction) to form sulfuric acidSodium residue.
However, the amount of sodium sulfate residue is now increasing (thousands of tons per year) and is often stored as waste in ponds or underground and can leak and contaminate the subsoil of disposal sites.
It is currently rarely recovered and added value in other industrial applications.
Background
US 5135734 discloses a sodium sulphate residue treatment process in which sodium sulphate is reacted with calcium chloride to produce calcium sulphate, which is stored underground in a salt cavity, and co-produces sodium chloride, which can be added value in an ammonia soda ash plant to produce sodium carbonate. However the volume amount of calcium sulphate exceeds the volume of sodium sulphate residues and therefore does not address problems related to disposal and leakage.
US 6180074 discloses a method of using a sodium sorbent made from sodium bicarbonate and a sodium ammonium compound. Sodium sulphate residues from flue gas abatement are dissolved and optionally treated with reactants to precipitate heavy metals on the main stream, but no mention is made of other compounds that accumulate in the loop and how to reduce purge volume. Furthermore, some ammonium compounds form complexes with certain heavy metals, such as copper, and produce a blue coloration on the resulting sodium sulfate, which is then hardly acceptable to other industrial users.
Thus, there is still a need to improve the prior art in order to reduce the purge volume and still produce sodium sulphate crystals of good quality, such as may be used by demanding industries, such as the detergent industry, the dye and textile industry and other industries, such as the glass industry.
The inventors of the present invention have found that sodium sulfate residues, particularly those used for flue gas SOx abatement, can be efficiently processed and purified while minimizing purging to obtain sodium sulfate that is marketable and minimizing the amount of final waste to be disposed of, which represents a significant advance over the prior art.
Disclosure of Invention
The present invention relates to an apparatus for recovering sodium sulphate from sodium sulphate waste, said sulphate waste comprising sodium sulphate, sodium carbonate and/or sodium bicarbonate, insoluble matter, and optionally: organic matter, sodium sulfite and/or sodium nitrite, the recovery apparatus includes:
(a) a dissolver (a) for dissolving sodium sulfate residues with a first aqueous solution to obtain a first aqueous suspension comprising sodium sulfate;
(b) separation means (B), such as: a filter, decanter or centrifuge for separating insoluble material from the first aqueous suspension by filtration, decantation or centrifugation to obtain:
-separated insoluble matter, and
-a second aqueous solution;
(c1) an acidification reactor (C1) for acidifying the second aqueous solution with sulfuric acid to a pH of less than 6, in order to convert at least part or all of the dissolved sodium carbonate and/or sodium bicarbonate into sodium sulfate;
(c2) an optional oxidation reactor (C2) for oxidizing the second aqueous solution with oxygen or air;
(c3) an alkalization reactor (C3) having a feed inlet for alkaline solids or alkaline solutions, such as sodium carbonate solids or solutions or sodium hydroxide solids or solutions, for alkalizing the aqueous solution leaving the acidification reactor (C1) or the optional oxidation reactor (C2) to a pH of about 7 or higher;
(d) an evaporator-crystallizer (D) for removing at least part of the water from the alkalinized aqueous solution leaving the alkalinizing reactor (C3) and obtaining a mother liquor and crystallizing sodium sulfate particles within said mother liquor;
(e) a separation device (E) for separating sodium sulfate particles from the mother liquor and recovering the sodium sulfate particles;
(f) purging means (F) within the evaporator-crystallizer (D) or within the separation device (E) for purging at least a portion of the mother liquor; and
(g) recycling means (G), such as a gravity tube outlet or a pump, for recycling at least a portion of the mother liquor not purged in at least one of these devices (a) to (D);
characterized in that the purge means (F) provides a purge weight ratio of purged separated mother liquor to un-purged separated mother liquor of at least 0.005t/t and at most 0.20 t/t.
A first advantage of the present invention is that purging is reduced by a factor of 4 to 10 compared to previous techniques for processing such residues.
A second advantage of the present invention is that the solids to be disposed of in, for example, underground mines are also reduced by a factor of 4 to 10 compared to previously known techniques.
A third advantage of the present invention is that it enables the size of the plant to be reduced by treating the mother liquor in which the impurities are concentrated, instead of treating the main stream after the sodium sulphate residue has dissolved.
A fourth advantage of the present invention is that it enables the production of high purity sodium sulfate with low organic and heavy metal content, especially when the sodium sulfate residue comes from DSI of the steel industry, coke industry and sintering plant, and is particularly suitable for use in the detergent industry and textile industry, while minimizing purge volume.
Drawings
Fig. 1 shows a representative scheme of a sodium sulfate recovery apparatus according to one embodiment of the present invention.
Detailed Description
In this specification, the plural and singular forms are used interchangeably. Thus, it is to be understood that the plural also includes the singular and vice versa.
The term "comprising" encompasses "consisting essentially of … … and" consisting of … … ".
The symbol "wt.%" refers to "weight percent" and the symbol "vol.%" refers to "volume percent". When vol.% is used for gas concentration, it is referred to herein as dry gas concentration (and thus no water vapor content).
The term "ppm" means parts per million by weight (e.g., 1 ppm-1 mg/kg).
In this specification, the description of a series of values for a variable bounded by a lower limit, or an upper limit, or by a lower limit and an upper limit, also includes embodiments in which the variable is correspondingly selected within the numerical range: the lower limit is not included, or the upper limit is not included, or both the lower limit and the upper limit are not included.
In addition, if the term "about" is used before a numerical value, then the present teachings also include the specific numerical value itself, unless expressly stated otherwise.
As used herein, the term "about" refers to a variation of ± 10% from the nominal value, unless explicitly stated otherwise.
The terms "soluble" and "insoluble" as used herein mean soluble or insoluble in aqueous solution, unless otherwise indicated. The term "soluble" denotes salts having a solubility in water equal to more than 0.05 g/l at 20 ℃. The term "insoluble" means a salt having a solubility in water of less than 0.05 g/l at 20 ℃.
Different embodiments of the invention relating to a sodium sulfate recovery plant (items 1 to 13) and to a method for purifying sodium sulfate residues (item 101 and subsequent items) are defined below. All items 1 to 13 and 101 to 123 of the present invention can be combined together.
Item 1. an apparatus for recovering sodium sulfate from sodium sulfate waste, the sodium sulfate waste comprising sodium sulfate, sodium carbonate and/or sodium bicarbonate, insoluble matter, and optionally: organic matter, sodium sulfite and/or sodium nitrite, the recovery apparatus includes:
(a) a dissolver (a) for dissolving sodium sulfate residues with a first aqueous solution to obtain a first aqueous suspension comprising sodium sulfate;
(b) separation means (B), such as: a filter, decanter or centrifuge for separating insoluble material from the first aqueous suspension by filtration, decantation or centrifugation to obtain:
-separated insoluble matter, and
-a second aqueous solution;
(c1) an acidification reactor (C1) for acidifying the second aqueous solution with sulfuric acid to a pH of less than 6, in order to convert at least part or all of the dissolved sodium carbonate and/or sodium bicarbonate into sodium sulfate;
(c2) an optional oxidation reactor (C2) for oxidizing the second aqueous solution with oxygen or air;
(c3) an alkalization reactor (C3) having a feed inlet for alkaline solids or alkaline solutions, such as sodium carbonate solids or solutions or sodium hydroxide solids or solutions, for alkalizing the aqueous solution leaving the acidification reactor (C1) or the optional oxidation reactor (C2) to a pH of about 7 or higher;
(d) an evaporator-crystallizer (D) for removing at least part of the water from the alkalinized aqueous solution leaving the alkalinizing reactor (C3) and obtaining a mother liquor and crystallizing sodium sulfate particles within said mother liquor;
(e) a separation device (E) for separating sodium sulfate particles from the mother liquor and recovering the sodium sulfate particles;
(f) purging means (F) within the evaporator-crystallizer (D) or within the separation device (E) for purging at least a portion of the mother liquor; and
(g) recycling means (G), such as a gravity tube outlet or a pump, for recycling at least a portion of the mother liquor not purged in at least one of these devices (a) to (D);
characterized in that the purge means (F) provides a purge weight ratio of purged separated mother liquor to un-purged separated mother liquor of at least 0.005t/t and at most 0.20 t/t.
(h1) an adsorption device (H1), such as an adsorption device comprising activated carbon, for adsorbing at least a portion of organic matter from the unblown separation mother liquor prior to recycling in at least one of these devices (A) to (G), and/or
(h2) A reactor (H2) for oxidizing at least part of the organic matter, the reactor having inlet means for introducing hydrogen peroxide or sodium hypochlorite,
to discolor the separated mother liquor not purged and/or to reduce its Total Organic Carbon (TOC) before recycling in at least one of these devices (a) to (G).
(i) at least one adding means (I) to the dissolver (a) and/or to the unblown separation mother liquor, such as a solid screw feeder or a pump, for adding at least one of the following reactants in solid form or in solution, before recycling in at least one of the means (a) to (H2):
hydroxide salts, such as: slaked lime (Ca (OH)2) Or caustic soda (NaOH);
silicates, such as sodium silicate or sodium metasilicate;
calcium salts, such as lime (CaO), anhydrous or hydrated calcium sulfate (CaSO)4) (hemihydrate or Gypsum Fibrosum), calcium chloride (CaCl)2) Calcium nitrate (Ca (NO)3)2)；
Sulfide salts, e.g. sodium sulfide (Na)2S), or organic sulfide compounds, such as TMT 15;
ferrous salts, e.g. ferrous sulfate (F)eSO4) Or iron salts, e.g. iron (Fe) sulfate2(SO4)3)；
Phosphates, such as alkali metal phosphates or alkaline earth metal phosphates;
lead salts, e.g. lead carbonate (PbCO)3)；
Or a mixture of these,
for precipitating at least part of a heavy metal or chemical element, such As aluminium (Al), arsenic (As), boron (B), barium (Ba), cadmium (Cd), chromium (Cr), iron (Fe), manganese (Mn), mercury (Hg), nickel (Ni), lead (Pb), antimony (Sb), selenium (Se), titanium (Ti), vanadium (V) or zinc (Zn), from the unblown separation mother liquor.
(j) Chloride analyzer means of the aqueous solution present in or exiting from any device or piece of equipment (a) to (I) and controlling the weight ratio of purged separated mother liquor to non-purged separated mother liquor such that the sodium chloride solution present in or exiting from the crystallization device (D) is at most 250g NaCl/kg mother liquor, preferably at most 220g NaCl/kg mother liquor.
k) a dryer (K), such as a spray dryer, is used to dry the purged isolated mother liquor to a salt powder.
Item 101. a process for purifying a sodium sulfate residue, the sodium sulfate residue comprising:
-at least 70 wt% of sodium sulphate,
-from 0.1 to 30 wt% of insoluble matter,
-from 0.1 to 30 wt% of sodium carbonate and/or sodium bicarbonate,
from 0.1 to 30% by weight of sodium chloride,
expressed in terms of the total weight of the residue,
the method comprises the following steps:
(a) dissolving the residue with a first aqueous solution to obtain a first aqueous suspension comprising at least 5 wt% and at most 32 wt% of sodium sulphate;
(b) optionally separating insoluble material from the first aqueous suspension by filtration, decantation or centrifugation to obtain:
-separated insoluble matter, and
-a second aqueous solution;
(c1) acidifying the second aqueous solution with sulfuric acid to a pH of less than 6 to convert at least part or all of the dissolved sodium carbonate and/or sodium bicarbonate to sodium sulfate;
(c2) optionally aerating the second aqueous solution with oxygen or air to convert sulfite to sulfate;
(c3) basifying the acidified second aqueous solution obtained in step (c1) to a pH of about 7 or higher using a base or alkaline solution such as sodium hydroxide or a portion of the second aqueous solution obtained in step (b);
(d) removing at least a portion of the water from the second aqueous solution from any of steps (c1) through (c3) to obtain a mother liquor, and crystallizing sodium sulfate particles within the mother liquor,
(e) separating the sodium sulfate particles from the mother liquor
(f) Purging at least a portion of the mother liquor and recycling at least a portion of the mother liquor not purged in at least one of the steps (a) to (d),
characterized in that the weight ratio of purged separation mother liquor to non-purged separation mother liquor is at most 0.20, preferably at most 0.10, more preferably at most 0.05t/t, or at most 0.005 t/t.
Item 102 the process of item 101, wherein the weight ratio of purged separation mother liquor to non-purged separation mother liquor is at least 0.001, preferably at least 0.002 t/t.
Item 103 the method of item 101 or 102, wherein the sodium sulfate residue comprises SO from the flue gasxAn abatement of residual salts, the flue gas being selected from: coking plants, sintering plants, steel plants, cement plants, glass plants, oil refineries, petrochemical plants, power plants, lime kilns, waste incinerators.
Item 104 the method of item 103, wherein the sodium sulfate residue comprises SO from the flue gasxReduction of residual salts from a coke plant or iron and steel plant or a sintering plant.
Item 105. the method of any of the preceding items, wherein the sodium sulfate residue is a salt residue obtained from flue gas abatement using dry sodium sorbent injection, such as sodium bicarbonate dry sorbent injection or trona dry sorbent injection.
Item 106. the method of any of the preceding items, wherein the sodium sulfate residue comprises from 0.05 to 10 wt.% sodium sulfite, and wherein step (c2) is performed so as to oxidize at least a portion of the sodium sulfite to sodium sulfate.
Item 107. the method of any of the preceding items, wherein the sodium sulfate residue comprises from 0.05 to 10 wt.% sodium nitrite, and wherein step (c2) is performed so as to oxidize at least a portion of the sodium nitrite to sodium nitrate.
Item 108. the method of any of the preceding items, wherein the unblown separated mother liquor is treated with at least one of the following treatments prior to recycling to any of steps (a) to (d):
-adsorbing at least a part of the dissolved organic matter on an adsorbent, such as activated carbon;
-adding an oxidant, such as hydrogen peroxide or sodium hypochlorite, to colour the separated mother liquor that has not been purged, and/or to reduce Total Organic Carbon (TOC);
or a mixture thereof.
Item 109. the method of any of the preceding items, wherein the unblown separated mother liquor is treated with at least one of the following chemicals in solid form or in solution prior to or while being recycled to any of steps (a) to (d):
hydroxide salts, such as: slaked lime (Ca (OH)2) Or caustic soda (NaOH);
silicates, such as sodium silicate or sodium metasilicate;
calcium salts, such as lime (CaO), anhydrous or hydrated calcium sulfate (CaSO)4) (hemihydrate or Gypsum Fibrosum), calcium chloride (CaCl)2) Calcium nitrate (Ca (NO)3)2)；
Sulfide salts, e.g. sodium sulfide (Na)2S), or organic sulfide compounds, such as TMT 15;
ferrous salts, e.g. ferrous sulphate (FeSO)4) Or iron salts, e.g. iron (Fe) sulfate2(SO4)3)；
Phosphates, such as alkali metal phosphates or alkaline earth metal phosphates;
lead salts, e.g. lead carbonate (PbCO)3)；
Or a mixture of these,
for precipitating at least part of heavy metals or chemical residual elements such As aluminium (Al), arsenic (As), boron (B), barium (Ba), cadmium (Cd), chromium (Cr), iron (Fe), manganese (Mn), mercury (Hg), nickel (Ni), lead (Pb), antimony (Sb), selenium (Se), titanium (Ti), vanadium (V) or zinc (Zn) from the unblown separation mother liquor.
Item 110. the method of item 109, wherein prior to or during recycling in step (a) or (b), and preferably at pH 7 to 11, or more preferably at pH 8 to 10, treatment with at least one of the following chemical agents is performed: hydroxide salts, silicates, calcium salts, sulfide salts, ferrous salts, phosphates, and mixtures thereof.
Item 111. the method of item 109, wherein prior to or during recycling in step (c) or (d), and preferably at pH 3 to 7, more preferably at pH 4 to 6, treatment with at least one of the following chemical agents is performed: iron or lead salts, hydroxide salts, silicates, calcium salts, sulfide salts, ferrous salts, phosphates and mixtures thereof.
Item 112. the method of any of the preceding items, wherein the purged mother liquor has a sodium sulfate concentration of at most 15 wt%, preferably at most 10 wt%, more preferably at most 8 wt%.
Item 113. the method of any of the preceding items, wherein the purged mother liquor has a sodium chloride concentration of at least 5 wt%, preferably at least 10 wt%, or at least 15 wt%.
Item 114. the method of any of the preceding items, wherein the purged mother liquor has a sodium chloride concentration of at most 28 wt%, preferably at most 25 wt%, or at most 20 wt%.
Item 115. the method of any of the preceding items, wherein the purged mother liquor is then spray dried.
Item 116. the method of any of the preceding items, further comprising:
(f) drying the sodium sulphate particles separated from the mother liquor in step (e).
Item 117. the method of any one of the preceding items, wherein the sodium sulfate particles obtained in step (d) are anhydrous sodium sulfate.
Item 118. the method of any one of items 101 to 116, wherein the sodium sulfate particles obtained in step (d) are sodium sulfate decahydrate crystals.
Item 119. the method of any of the preceding items, wherein the sodium sulfate particles are further used as a sodium feedstock in a soda ash plant.
Item 120. the method of the previous item, wherein the sodium sulfate particles are further dissolved and reacted with residual distillate from the ammonia soda ash process comprising calcium chloride to produce sodium chloride and calcium sulfate, and the sodium chloride is further recycled to produce sodium carbonate or sodium bicarbonate.
Item 121. use of the sodium sulfate particles obtained from step (e) or (f) of any of the preceding items in a detergent powder or a detergent tablet.
Item 122. use of the sodium sulfate particles obtained from step (e) or (f) of any one of items 101 to 120 in a glass furnace.
Item 123 use of the sodium sulfate particles obtained from step (e) or (f) of any one of items 101 to 120 in a dyeing and/or textile process.
FIG. 1 illustrates an embodiment of the sodium sulfate recovery apparatus of the present invention. Dissolving sodium sulphate waste 0 comprising sodium sulphate, sodium carbonate and insoluble matter in a dissolver (a) for dissolving sodium sulphate residues with a first aqueous solution 1 to obtain a first aqueous suspension 2 comprising sodium sulphate and sodium carbonate, and injecting it into a filter press (B) to separate separated insoluble matter 4 and a second aqueous solution 3; said second aqueous solution 3 is then introduced into an acidification reactor (C1) for acidification of this second aqueous solution with sulfuric acid 5 to a pH of less than 6, in order to convert all the dissolved sodium carbonate into sodium sulfate; removing CO produced by acidifying carbonate from reactor (C1) through outlet placed on reactor2(ii) a The acidified second aqueous solution 6 is then fed to an alkalization reactor (C3) with a reactor for alkaline solids or alkaline solutions such as carbonic acidA feed inlet for sodium solids or solution or sodium hydroxide solids or solution 7 for basifying the aqueous solution leaving the acidification reactor (C1) to a pH of about 7 or higher; an evaporator-crystallizer (D) for removing at least a portion of the water 9 from the alkalinized aqueous solution leaving the alkalinizing reactor (C3) and obtaining a mother liquor and crystallizing sodium sulfate particles within the mother liquor; a separation device (E) for separating the sodium sulfate particles 15 from the mother liquor 11 and recovering the sodium sulfate particles 15; purging means (F), such as a pump, capable of purging a portion of the mother liquor to maintain the level of soluble impurities in the crystallizer at a target value, said purging means (F) being placed on the pipe from the filter press (E) to the evaporator-crystallizer (D) for recycling the mother liquor 13 and for recycling the mother liquor 14 to the dissolver (a); pump (F) is selected to provide a purge weight ratio of purged separation mother liquor 12 to un-purged separation mother liquor (13+14) of at least 0.005t/t and at most 0.20 t/t.
If the disclosure of any patent, patent application, and publication incorporated by reference herein conflicts with the description of the present application to the extent that terminology may become unclear, the description shall take precedence.
Examples of the invention
The following examples are intended to illustrate the invention without limiting its scope.
The samples used hereinafter were selected from different steel works and coke plant dry sorbent injection flue gas abatement using technical grade sodium bicarbonate.
Typical analysis of sodium sulfate residues (e.g., coking flue gas abatement residues) is present on the market.
TABLE 1 main component of coking residue
As shown in table 1, the sulfate residue was an inorganic residue, and most of the content in the residue was Na2SO4. Due to insufficient reaction, 10% to 15% of Na still remains in the residue2CO3. However, in order toMixing Na2CO3Conversion to Na2SO4By H2SO4Acid etching is performed and thus more than 95% of Na is obtained2SO4And (4) content.
In the following examples, samples were tested for residual analysis in order to illustrate the present invention.
Table 2 values of key components (composition in wt%) in the three batches of residue.
The following steps were carried out on a laboratory scale on a reactor of 1.5 liter volume:
dissolution → filtration → acidification → crystallization → drying
The sodium sulfate residue was first dissolved in water and formed a yellow liquid (i.e., a first aqueous suspension) with black insoluble particles. The solution has a concentration of 25 wt% calculated as salt, is nearly saturated at room temperature, and comprises Na2CO3、Na2SO4NaCl, and insoluble particles. A filtration step was performed on a laboratory filter to remove insoluble particles, so that the resulting solution (i.e. 'second aqueous solution') included Na2CO3、Na2SO4And NaCl.
Then, H is added at a pH below 3.72SO4Added to the solution to add all Na2CO3Conversion to Na2SO4And then NaOH is added to adjust the pH back to 7-8 so that after the acidification and neutralization process the solution has its sodium carbonate converted to sodium sulfate and thus mainly comprises Na2SO4、NaCl。
After the above step, the second aqueous solution was injected into the flask for the crystallization process. The crystallization process was maintained at 50 ℃ and a pressure of 100 mbar. The evaporation rate was 100g water/h. During evaporation, when saturation is reached, Na2SO4And (4) crystallizing.
After a certain crystallization period, the crystal particles are removed from the solutionAnd then dried in an oven after washing. The resulting purified Na2SO4Showing a very light color.
In addition, the COD content and Na were also taken into account during the whole process2SO3. Due to Na under acidic pH2SO3Oxidized to Na2SO4It is low in solution. The COD content in the solution before crystallization was 150-300ppm equivalent carbon. COD from the organics does not evaporate in the crystallization step, so it accumulates when the mother liquor of the crystallization is recycled to re-dissolve the sodium sulfate residue. To avoid high concentrations of impurities such as sodium chloride or organics, the purge (purge) is treated on activated carbon and/or with H2O2Or hypochlorite oxidation to remove a portion of the organics (as measured by COD or TOC) rather than purging a large volume of crystallization mother liquor. And a portion of this treated mother liquor is recycled back to the dissolution of the sodium sulphate residue according to the invention.
The purified sodium sulphate obtained was colourless, as when the purge from the crystalliser was not treated, the sodium sulphate particles obtained became increasingly brown.
In addition, examination of the heavy metal concentrations in the final sodium sulfate, and the listed elements of the reactants, such as sodium silicate or sodium sulfide, shows that heavy metal removal from the concentrated crystallization mother liquor is more effective and reduced for total weight metal removal than from the main dissolution flow stream.
Treatment of the purge can sensitively reduce the purge volume and increase the yield of sodium sulfate recovered from the residue and reduce the purge brine to be disposed.
The final crystalline sodium sulfate meets the Chinese national standard (class II first grade).
Another test was to heat the crystallizer with a higher temperature difference (60 ℃) and have a higher evaporation rate of 300g water/h (compared to 100g/h with a lower temperature difference: 25 ℃). The crystals obtained have a smaller size compared to previous tests, but still meet the chinese national standard (class II first).
Testing of other sodium sulphate residues with similar composition but from other industrial flue gases (power steam generator, tyre incinerator.) shows similar behaviour with respect to the possibility of limiting the purge amount when purifying a portion of the purge of the mother liquor before recycling it in the crystallizer or in the dissolution step. Although the level of impurities in the sulfate residue varies depending on the flue gas type, and thus the result is to adjust the amount of sorbent or reactant to remove the impurities. The steel and coke residues in the sulphate residues present advantageous conditions for obtaining highly purified sodium sulphate particles.
Claims (30)
1. A sodium sulfate recovery apparatus for recovering sodium sulfate from sodium sulfate waste, the sodium sulfate recovery apparatus comprising:
(a) a dissolver (a) for dissolving sodium sulfate residues with a first aqueous solution to obtain a first aqueous suspension comprising sodium sulfate;
(b) first separation means (B) for separating insoluble matter from the first aqueous suspension by filtration, decantation or centrifugation to obtain:
-separated insoluble matter, and
-a second aqueous solution;
(c1) an acidification reactor (C1) for acidifying the second aqueous solution with sulfuric acid to a pH of less than 6, in order to convert at least part or all of the dissolved sodium carbonate and/or sodium bicarbonate into sodium sulfate;
(c2) an optional oxidation reactor (C2) for oxidizing the second aqueous solution with oxygen or air;
(c3) an alkalization reactor (C3) having a feed inlet for alkaline solids or alkaline solution for alkalizing the aqueous solution leaving the acidification reactor (C1) or the optional oxidation reactor (C2) to a pH of about 7 or higher;
(d) an evaporator-crystallizer (D) for removing at least part of the water from the alkalinized aqueous solution leaving the alkalinizing reactor (C3) and obtaining a mother liquor and crystallizing sodium sulfate particles within said mother liquor;
(e) second separating means (E) for separating sodium sulfate particles from the mother liquor and recovering the sodium sulfate particles;
(f) purging means (F) within the evaporator-crystallizer (D) or within the second separation device (E) for purging at least a portion of the mother liquor; and
(g) recycling means (G) for recycling at least a portion of the mother liquor not purged in at least one of the following devices: a dissolver (a), a first separation device (B), an acidification reactor (C1), an optional oxidation reactor (C2), an alkalization reactor (C3), an evaporator-crystallizer (D);
characterized in that the purge means (F) provides a purge weight ratio of purged separated mother liquor to un-purged separated mother liquor of at least 0.005 and at most 0.20.
2. The sodium sulfate recovery plant according to claim 1, wherein the purge means (F) provides a purge weight ratio of purged separated mother liquor to un-purged separated mother liquor of at most 0.10.
3. The sodium sulfate recovery plant of claim 2 wherein the purge means (F) provides a purge weight ratio of purged separated mother liquor to un-purged separated mother liquor of at most 0.05.
4. The sodium sulfate recovery apparatus of claim 1, adapted to treat sodium sulfate residue comprising SO from flue gasxAn abatement of residual salts, the flue gas being selected from: coking plants, sintering plants, steel plants, cement plants, glass plants, oil refineries, petrochemical plants, power plants, lime kilns, waste incinerators.
5. The sodium sulfate recovery apparatus of claim 4, wherein said flue gas is selected from the group consisting of a coke plant, a sinter plant, and a steel plant.
6. The sodium sulfate recovery apparatus of claim 4, adapted to treat sodium sulfate residue obtained from flue gas abatement using a dry sodium sorbent injection process.
7. The sodium sulfate recovery apparatus of claim 6, wherein the sodium sorbent is selected from sodium bicarbonate or trona.
8. The sodium sulfate recovery apparatus of claim 1, further comprising at least one of the following:
(h1) an adsorption device (H1) for adsorbing at least a part of the organic matter from the separation mother liquor not purged before recycling in at least one of the dissolver (A), the first separation device (B), the acidification reactor (C1), the oxidation reactor (C2), the alkalization reactor (C3), the evaporator-crystallizer (D), the second separation device (E), the purging means (F), the recycling means (G), and/or
(h2) A reactor (H2) for oxidizing at least part of the organic matter, the reactor having inlet means for introducing hydrogen peroxide or sodium hypochlorite,
to color and/or reduce the Total Organic Carbon (TOC) of the separated mother liquor not purged before recycling in at least one of the dissolver (a), the first separation device (B), the acidification reactor (C1), the oxidation reactor (C2), the alkalization reactor (C3), the evaporator-crystallizer (D), the second separation device (E), the purging means (F), the recycling means (G).
9. The sodium sulfate recovery apparatus of claim 1, further comprising:
(i) at least one first addition means (I1) for adding at least one of the following reactants in solid form or in solution to the dissolver (a) and before recycling in at least one of the dissolver (a), the first separation device (B), the acidification reactor (C1), the oxidation reactor (C2), the alkalization reactor (C3), the evaporator-crystallizer (D), the second separation device (E), the purging means (F), the recycling means (G), the adsorption means (H1), the reactor (H2), to the separation mother liquor that has not been purged:
-a hydroxide salt;
-a silicate;
-a calcium salt;
-a sulfide salt or an organic sulfide compound;
-a ferrous salt;
-a phosphate;
-a lead salt;
for precipitating at least a portion of the heavy metal or chemical element from the unblown separation mother liquor.
10. The sodium sulfate recovery apparatus of claim 1, further comprising:
(i) second adding means (I2) for adding at least one of the following reactants in solid form or in solution to the dissolver (a) or to the unblown separation mother liquor before recycling in at least one of dissolver (a), first separating device (B), acidification reactor (C1), oxidation reactor (C2), basification reactor (C3), evaporator-crystallizer (D), second separating device (E), purging means (F), recycling means (G), adsorption means (H1), reactor (H2):
-a hydroxide salt;
-a silicate;
-a calcium salt;
-a sulfide salt or an organic sulfide compound;
-a ferrous salt;
-a phosphate;
-a lead salt;
for precipitating at least a portion of the heavy metal or chemical element from the unblown separation mother liquor.
11. The sodium sulfate recovery apparatus of claim 10, wherein the first separation device (B) is adapted to separate heavy metal precipitates or chemical element precipitates produced by the means (I) for adding the at least one reactant, when said reactant is added to the dissolver (a) and/or to the unblown separation mother liquor, before recycling in at least one of dissolver (a), first separation device (B), acidification reactor (C1), oxidation reactor (C2), alkalization reactor (C3), evaporator-crystallizer (D), second separation device (E), purging means (F), recycling means (G), adsorption means (H1), reactor (H2).
12. The sodium sulfate recovery apparatus of claim 1, wherein the evaporator-crystallizer (D) is of forced circulation evaporator-crystallizer type or of draft tube baffle evaporator-crystallizer type.
13. The sodium sulfate recovery apparatus of claim 1, which is used to process sodium sulfate residue comprising sodium chloride, and further comprising:
(j) for being present in any of dissolver (A), first separating device (B), acidification reactor (C1), oxidation reactor (C2), alkalization reactor (C3), evaporator-crystallizer (D), second separating device (E), purging means (F), recycling means (G), adsorption means (H1), reactor (H2), first adding means (I1) and second adding means (I2) or dissolver (A), first separating device (B), acidification reactor (C1), oxidation reactor (C2), alkalization reactor (C3), evaporator-crystallizer (D), second separating device (E), purging means (F), recycling means (G), adsorption means (H1), reactor (H2), first adding means (I1) and second adding means (I2), or the aqueous solution exiting therefrom, and controlling the weight ratio of the purged separation mother liquor to the non-purged separation mother liquor such that the sodium chloride solution present in the crystallization device (D) or in the mother liquor exiting the crystallization device (D) is at most 250g NaCl/kg mother liquor.
14. The sodium sulfate recovery apparatus of claim 13, wherein the weight ratio of purged separation mother liquor to non-purged separation mother liquor is controlled such that the sodium chloride solution present in the crystallization device (D) or in the mother liquor leaving the crystallization device (D) is at most 220g NaCl/kg mother liquor.
15. The sodium sulfate recovery apparatus of claim 13, wherein the weight ratio of purged separation mother liquor to un-purged separation mother liquor is controlled such that the weight ratio of sodium chloride to sodium sulfate in the purged separation mother liquor is at least 1.5 and at most 6.
16. The sodium sulfate recovery apparatus of claim 15, wherein the weight ratio of purged separation mother liquor to un-purged separation mother liquor is controlled such that the weight ratio of sodium chloride to sodium sulfate in the purged separation mother liquor is at least 2.5 and at most 4.
17. The sodium sulfate recovery apparatus of claim 1 or claim 15, further comprising:
k) a dryer (K) for drying the purged separated mother liquor to a salt powder.
18. The sodium sulfate recovery apparatus of claim 12, wherein the evaporator-crystallizer (D) operates under vacuum.
19. The sodium sulfate recovery apparatus of claim 12, wherein the evaporator-crystallizer (D) operates at a temperature from 50 ℃ to 120 ℃.
20. The sodium sulfate recovery apparatus of claim 9 or 10, wherein the hydroxide salt is slaked lime (ca (oh))2) Or caustic soda (NaOH).
21. The sodium sulfate recovery apparatus of claim 9 or 10, wherein the silicate is sodium silicate or sodium metasilicate.
22. A sodium sulphate recovery apparatus according to claim 9 or claim 10 wherein the calcium salt is lime (CaO), anhydrous or hydrated calcium sulphate (CaSO)4) Calcium chloride (CaCl)2) Nitric acid, nitric acidCalcium (Ca (NO)3)2）。
23. The sodium sulfate recovery apparatus of claim 9 or 10, wherein the sulfide salt is sodium sulfide (Na)2S）。
24. The sodium sulfate recovery apparatus of claim 9 or 10, wherein the organosulfide compound is TMT 15.
25. The sodium sulfate recovery apparatus of claim 9 or 10, wherein the ferrous salt is ferrous sulfate (FeSO)4）。
26. The sodium sulfate recovery apparatus of claim 9 or 10, wherein the iron salt is iron sulfate (Fe)2(SO4)3）。
27. The sodium sulfate recovery apparatus of claim 9 or 10, wherein the phosphate is an alkali metal phosphate or an alkaline earth metal phosphate.
28. The sodium sulfate recovery apparatus of claim 9 or 10, wherein the lead salt is lead carbonate (PbCO)3）。
29. The sodium sulfate recovery apparatus of claim 9 or 10, wherein the heavy metal or chemical element is aluminum (Al), arsenic (As), boron (B), barium (Ba), cadmium (Cd), chromium (Cr), iron (Fe), manganese (Mn), mercury (Hg), nickel (Ni), lead (Pb), antimony (Sb), selenium (Se), titanium (Ti), vanadium (V), or zinc (Zn).
30. The sodium sulfate recovery apparatus of claim 1, wherein the feed inlet is for a sodium carbonate solid or solution or a sodium hydroxide solid or solution.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201920741030.6U CN212315566U (en) | 2019-05-22 | 2019-05-22 | Sodium sulfate recovery plant |
| PCT/CN2020/090982 WO2020233558A1 (en) | 2019-05-22 | 2020-05-19 | Process for purifying a sodium sulfate residue |
| KR1020217041435A KR20220034732A (en) | 2019-05-22 | 2020-05-19 | Purification process of sodium sulfate residue |
| CN202080037986.3A CN113874322B (en) | 2019-05-22 | 2020-05-19 | Method for purifying sodium sulfate residue |
| EP20809363.3A EP3972936A4 (en) | 2019-05-22 | 2020-05-19 | Process for purifying a sodium sulfate residue |
| CN202311265402.XA CN117326574A (en) | 2019-05-22 | 2020-05-19 | Method for purifying sodium sulfate residue |
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| CN201920741030.6U CN212315566U (en) | 2019-05-22 | 2019-05-22 | Sodium sulfate recovery plant |
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| CN114261978A (en) * | 2021-12-22 | 2022-04-01 | 四川省洪雅青衣江元明粉有限公司 | Efficient purification method of saltpeter water |
| CN115350500B (en) * | 2022-08-23 | 2023-10-13 | 宁夏日盛高新产业股份有限公司 | Byproduct comprehensive utilization system in foaming agent production |
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| FR2638108B1 (en) | 1988-10-26 | 1991-02-08 | Solvay | PROCESS FOR REMOVING A RESIDUE COMPRISING SODIUM SULFATE |
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| KR100582801B1 (en) * | 2003-10-13 | 2006-05-23 | 요업기술원 | Refining method of high purified sodium sulfate from wasted sodium sulfate arising from electric precipitator |
| WO2009078690A1 (en) * | 2007-12-14 | 2009-06-25 | Servicios Industriales Peñoles S.A. de C.V. | Method for the production of sodium sulphate and magnesium hydroxide |
| TR201108573T1 (en) * | 2009-03-06 | 2012-01-23 | Solvay Chemicals, Inc. | Removal of impurities in the production of crystalline sodium carbonate, bicarbonate or sulfite. |
| WO2011138005A1 (en) * | 2010-05-04 | 2011-11-10 | Solvay Chemicals, Inc. | Impurities removal from waste solids in the production of soda ash, sodium bicarbonate and/or other derivatives |
| US20130072371A1 (en) * | 2011-03-17 | 2013-03-21 | Ppg Industries Ohio, Inc. | Method of, and apparatus for, using a glass fluxing agent to reduce foam during melting of glass batch |
| CN103450287B (en) * | 2013-09-24 | 2015-09-23 | 山东华义玉米科技有限公司 | A kind of glucose mother liquid recycling technique |
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| CN105906126A (en) * | 2016-06-12 | 2016-08-31 | 双良节能系统股份有限公司 | Salt-containing wastewater resource recycling and disposal system and method |
| CN108658353B (en) * | 2018-06-08 | 2021-06-18 | 石家庄工大科技开发有限公司 | Calcium chloride wastewater treatment process |
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| CN113874322A (en) | 2021-12-31 |
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| EP3972936A1 (en) | 2022-03-30 |
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