CN103588340A - Method for treating sodium-alkali desulfurization waste liquid by causticization-acidification method - Google Patents
Method for treating sodium-alkali desulfurization waste liquid by causticization-acidification method Download PDFInfo
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- CN103588340A CN103588340A CN201310609080.6A CN201310609080A CN103588340A CN 103588340 A CN103588340 A CN 103588340A CN 201310609080 A CN201310609080 A CN 201310609080A CN 103588340 A CN103588340 A CN 103588340A
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- sodium
- waste liquid
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- calcium
- thiocyanate
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- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 36
- 230000023556 desulfurization Effects 0.000 title claims abstract description 36
- 239000007788 liquid Substances 0.000 title claims abstract description 36
- 239000003513 alkali Substances 0.000 title claims abstract description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 107
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims abstract description 52
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 46
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000011734 sodium Substances 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 13
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 13
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims abstract description 12
- 235000010261 calcium sulphite Nutrition 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims abstract 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims abstract 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 85
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 42
- 239000000706 filtrate Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 23
- 238000002425 crystallisation Methods 0.000 claims description 17
- 235000010265 sodium sulphite Nutrition 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002535 acidifier Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003546 flue gas Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical group [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 239000000571 coke Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- -1 hydroxide ions Chemical class 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 3
- 239000001569 carbon dioxide Substances 0.000 claims 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims 1
- 235000011941 Tilia x europaea Nutrition 0.000 claims 1
- 239000004571 lime Substances 0.000 claims 1
- 239000008267 milk Substances 0.000 claims 1
- 210000004080 milk Anatomy 0.000 claims 1
- 235000013336 milk Nutrition 0.000 claims 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 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 9
- 229910052708 sodium Inorganic materials 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000001704 evaporation Methods 0.000 abstract description 6
- 230000008020 evaporation Effects 0.000 abstract description 5
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 abstract description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000003034 coal gas Substances 0.000 abstract description 2
- 238000004042 decolorization Methods 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 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 13
- 239000000047 product Substances 0.000 description 12
- 238000009993 causticizing Methods 0.000 description 10
- JNVCSEDACVAATK-UHFFFAOYSA-L [Ca+2].[S-]SSS[S-] Chemical compound [Ca+2].[S-]SSS[S-] JNVCSEDACVAATK-UHFFFAOYSA-L 0.000 description 9
- 235000011116 calcium hydroxide Nutrition 0.000 description 9
- 239000012530 fluid Substances 0.000 description 9
- 229940051851 sulfurated lime Drugs 0.000 description 9
- 235000011089 carbon dioxide Nutrition 0.000 description 8
- 229920001021 polysulfide Polymers 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
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- Treating Waste Gases (AREA)
- Removal Of Specific Substances (AREA)
Abstract
本发明公开一种用苛化-酸化法处理钠碱法脱硫废液的方法，属于脱硫废液处理技术领域。本发明方法包括废液预处理除杂质、加热分解脱色、氧化苛化－分离、酸化－分离、蒸发浓缩以及冷却结晶－分离工艺过程。本发明方法用于处理钠碱法脱除煤气或其他气体中硫化氢、氰化氢工艺产生的脱硫废液，该方法能够在常温条件下，通过加热分解、氧化、苛化将钠碱法脱硫废液中的硫代硫酸钠、多硫化钠、硫酸钠转化成亚硫酸钙、硫化钙和硫酸钙沉淀，同时提取高纯度的碳酸钠和硫氰酸钠，回收钠碱重新返回脱硫系统循环，降低脱硫操作的碱耗。
The invention discloses a method for treating sodium-alkali desulfurization waste liquid by a causticization-acidification method, and belongs to the technical field of desulfurization waste liquid treatment. The method of the invention comprises waste liquid pretreatment to remove impurities, heat decomposition and decolorization, oxidative causticization-separation, acidification-separation, evaporation concentration and cooling crystallization-separation process. The method of the present invention is used to treat the desulfurization waste liquid produced by the process of removing hydrogen sulfide and hydrogen cyanide in coal gas or other gases by sodium-alkali method, and the method can desulfurize the sodium-alkali method through thermal decomposition, oxidation and causticization under normal temperature conditions Sodium thiosulfate, sodium polysulfide, and sodium sulfate in the waste liquid are converted into calcium sulfite, calcium sulfide, and calcium sulfate precipitates, and high-purity sodium carbonate and sodium thiocyanate are extracted at the same time, and the recovered sodium alkali is returned to the desulfurization system for circulation. Reduce the alkali consumption of desulfurization operation.
Description
Technical field:
The invention belongs to desulfurization waste liquor processing technology field, be specifically related to a kind of method of processing soda method desulfurization waste liquor with causticization-acidization.
Background technology:
In the chemical fields such as Coal Chemical Industry, petrochemical complex and Sweet natural gas, gas adopts Wet Catalytic Oxidation Method technique to remove hydrogen sulfide, the feature of its technique is that the hydrogen sulfide of absorption is catalytically converted into sulfur foam, separate out the water of equimolecular number, due to system, there is element or the compounds such as prussic acid, oxygen, sulphur, alkali simultaneously, therefore the side reaction of salt occurs to generate simultaneously.The secondary salt generating during as alkali source with sodium carbonate is mainly Sodium Thiocyanate 99, Sulfothiorine, sodium polysulphide, sodium sulfate etc., the accumulation of side reaction salt declines the receptivity of doctor solution, so outer row partly contains the doctor solution (being commonly called as desulfurization waste liquor) of secondary salt continuously, and supplementary new doctor solution maintains quality and the sweetening power of doctor solution to alleviate the load of secondary salt.Outer row must be through processing containing the desulfurization waste liquor of secondary salt, and desulfurization waste liquor contaminate environment and the water body of untreated direct discharge, have strong corrosive power to hardware.The treatment process of existing soda method desulfurization waste liquor is mainly as follows:
1, the method for treating waste liquid matching with modified ADA desulfurizer technique, is to adopt substep evaporating, concentrating and crystallizing method to extract Sulfothiorine and Sodium Thiocyanate 99 coarse products, and the method is also called " freezing Steppecd crystallization " technique.The method feature is first to carry out vacuum evaporation, then Vacuum Heat filters except carbonic acid sodium impurity, filtrate is cooled to-5 ℃ with refrigerated water, separate out Sulfothiorine crystallization, through centrifugation, extract the thick product of Sulfothiorine, remove filtrate after Sulfothiorine as the raw material that extracts Sodium Thiocyanate 99, by the same method, extract rough Sodium Thiocyanate 99.The method requires to adopt the refrigerated water cooling concentration liquid of-5 ℃ to make Sulfothiorine crystallization, so processing unit configuration is many, needs auxiliary construction refrigerator device, long flow path, power consumption is high, and concentrated solution forms complicated, and crystallized product impurity is many, be difficult for primary crystallization acquisition straight product.
2, Japan's " ammonia type-Taka Haake this " sulfur removal technology mainly adopts the uncommon Luo Hakesi process for treating waste liquor that is called " wet oxidation process ", and final product is ammonium sulfate.And Japan's " sodium type-Taka Haake this " sulfur removal technology liquid waste disposal is mainly to adopt " reduction combustion method " burning waste liquid and sulphur, final product is sulfuric acid and sodium carbonate.The shortcoming of the method is that process for treating waste liquor route is long, and added value of product is not high, and production equipment construction cost and maintenance cost are high, so overall economic benefit is low, in waste liquid, more valuable Sodium Thiocyanate 99 does not reclaim in addition.
Summary of the invention:
The present invention is directed to the problem existing in existing soda method desulfurization waste liquor treatment process, a kind of method of processing soda method desulfurization waste liquor with causticization-acidization is provided.
A kind of method concrete steps with causticization-acidization processing soda method desulfurization waste liquor provided by the present invention are as follows:
(1) at normal temperatures and pressures, use entrained solid impurity in the sorbing material fractionation by adsorption soda method desulfurization waste liquors such as coke or gac;
(2) the soda method desulfurization waste liquor after described step (1) is processed is through evaporation concentration, make unsettled Sulfothiorine and sodium polysulphide in waste liquid be decomposed into respectively S-WAT and sodium sulphite, and when separating out elemental sulfur, to being blown into pressurized air in described soda method desulfurization waste liquor, carry out oxidizing reaction, make through decomposing the S-WAT and the sodium sulphite that produce, to be oxidized to sodium sulfate in described soda method desulfurization waste liquor, the temperature of described thermolysis-oxidizing reaction is 85～125 ℃, the volume that described pressurized air is blown into is 20～160 times of described soda method desulfurization waste liquor volume,
(3) step (2), after the soda method desulfurization waste liquor filtering and impurity removing after thermolysis-oxidizing reaction is processed, is added to milk of lime Ca (OH) in filtrate
2carry out causticizing reaction, the temperature of causticizing reaction is 85～125 ℃, makes the sodium sulfate Na in filtrate
2sO
4and remaining S-WAT Na
2sO
3with sodium sulphite Na
2s changes into respectively calcium sulfate and calcium sulfite and sulfurated lime precipitation, and sodium ion reacts with hydroxide ion and generates sodium hydroxide, by after calcium sulfite, sulfurated lime and calcium sulfate filtering, and the filtrate that obtains being rich in Sodium Thiocyanate 99 and sodium hydroxide;
(4) filtrate of being rich in Sodium Thiocyanate 99 and sodium hydroxide step (3) being obtained is placed in acidifier, in described acidifier, be blown into the stack gas through purifying, make carbonic acid gas in described stack gas with described in be rich in the sodium hydroxide generation neutralization reaction in the filtrate of Sodium Thiocyanate 99 and sodium hydroxide, reaction product is sodium bicarbonate, the sodium bicarbonate that neutralization reaction generates further reacts generation sodium carbonate with the sodium hydroxide that described step (3) causticizing reaction generates, simultaneously, carbonic acid gas in described purifying flue gas with described in be rich in calcium hydroxide reaction residual in the filtrate of Sodium Thiocyanate 99 and sodium hydroxide and generate precipitation of calcium carbonate, reacted filtrate is removed by filter to the acidizing fluid that obtains being rich in Sodium Thiocyanate 99 and sodium carbonate after precipitation of calcium carbonate,
(5) acidizing fluid that is rich in Sodium Thiocyanate 99 and sodium carbonate step (4) being obtained is put into the first crystallisation by cooling groove through heating after solid impurity is removed in concentrated and charcoal absorption, by the water at low temperature that temperature is 18～25 ℃, be cooled to 35～45 ℃, after cool slurry, separate out crystals of sodium carbonate, the slurries that contain crystals of sodium carbonate are put into sodium carbonate centrifugal filter and filter out crystals of sodium carbonate;
(6) filtrate step (5) being filtered out after crystals of sodium carbonate is put into the second crystallisation by cooling groove, by the water at low temperature that temperature is 18～25 ℃, be cooled to 25～30 ℃, separate out Sodium Thiocyanate 99 crystal, the slurry impouring Sodium Thiocyanate 99 centrifugal filter that contains Sodium Thiocyanate 99 crystal is filtered, obtain Sodium Thiocyanate 99 crystal;
(7) filtrate filtering out after Sodium Thiocyanate 99 crystal is returned to desulphurization system.
The related principles of chemistry of the inventive method are specific as follows:
First solution is heated to concentration, make the compound decomposition such as unsettled sodium polysulphide, Sulfothiorine separate out elemental sulfur, generate S-WAT, sodium sulphite etc., the atmospheric oxidation being then blown into generates sodium sulfate.
Na
2S
2O
3 === Na
2SO
3 + S
Na
2Sx+1=== Na
2S + xS
2Na
2SO
3 + O
2=== 2Na
2SO
4
Na
2S + 2O
2=== Na
2SO
4
With milk of lime Ca (OH)
2by the sodium sulfate N in waste liquid
a2sO
4and remaining S-WAT N
a2sO
3with sodium sulphite N
a2s carries out respectively causticizing reaction and changes into calcium sulfate and calcium sulfite and sulfurated lime precipitation, and sodium ion reacts with hydroxide ion and generates sodium hydroxide, by after calcium sulfite, sulfurated lime and calcium sulfate filtering, and the filtrate that obtains being rich in Sodium Thiocyanate 99 and sodium hydroxide.
Na
2SO
3+Ca(OH)
2== CaSO
3 ↓+ 2NaOH
Na
2SO
4 +Ca(OH)
2 == CaSO
4↓
+ 2NaOH
Na
2S + Ca(OH)
2 === CaS↓+ 2NaOH
Because Sodium Thiocyanate 99 and calcium hydroxide do not react, so only deposit sodium hydroxide and Sodium Thiocyanate 99 and a small amount of superfluous calcium hydroxide in the solution after sediment separate out.Then the filtrate after filtering precipitate is placed in acidifier, and be blown into the stack gas through purifying in acidifier, make the carbonic acid gas in stack gas and be rich in the sodium hydroxide generation neutralization reaction in Sodium Thiocyanate 99 and sodium hydroxide filtrate, generate sodium bicarbonate, further there is causticizing reaction and generate sodium carbonate in sodium bicarbonate and carbonic acid gas, simultaneously, in carbonic acid gas in purifying flue gas and filtrate, residual calcium hydroxide reaction generates precipitation of calcium carbonate, reacted filtrate is removed by filter to the acidizing fluid that obtains being rich in Sodium Thiocyanate 99 and sodium carbonate after precipitation of calcium carbonate.
CO
2 + Ca(OH)
2 == CaCO
3 ↓ + H
2O
CO
2 + NaOH == NaHCO
3
NaHCO
3+ NaOH == Na
2CO
3 +H
2O
The acidizing fluid that is rich in Sodium Thiocyanate 99 and sodium carbonate is removed to solid impurity through heating concentrated and charcoal absorption.
Because the dissolubility difference of sodium carbonate and two kinds of compound crystals of Sodium Thiocyanate 99 is larger, can adopt crystallisation by cooling method successively to extract respectively sodium carbonate and Sodium Thiocyanate 99 crystal product, sodium carbonate returns to desulphurization circulating liquid system, and Sodium Thiocyanate 99 crystal is as the finished product export trade.
The inventive method comprises following process links: waste liquid pretreatment impurity removing, thermal degradation decolouring, oxidation causticization-separation, acidifying-separation, evaporation concentration, crystallisation by cooling-separation.
" waste liquid pretreatment process " is to remove the organic or inorganic solid impurity entering at random in waste liquid, as sulphur, tar, ferruginization compound.
" thermal degradation bleaching process " is that thermolysis Sulfothiorine and sodium polysulphide are separated out elemental sulfur and S-WAT and sodium sulphite, and removes catalyst residue, and solution is become colorless.
" oxidation causticization-separation circuit " is to be oxidized to sodium sulfate with S-WAT and sodium sulphite that air generates " thermal degradation bleaching process "; With milk of lime Ca (OH)
2with sodium sulfate N
a2sO
4and remaining S-WAT N
a2sO
3with sodium sulphite N
a2s carries out respectively causticizing reaction and generates calcium sulfate and calcium sulfite and sulfurated lime precipitation; Sodium ion in solution reacts with hydroxide ion and generates sodium hydroxide; By after calcium sulfite, sulfurated lime and calcium sulfate filtering, the filtrate that obtains being rich in Sodium Thiocyanate 99 and sodium hydroxide.
" acidifying-separation circuit " is the filtrate after separated with causticizing reaction in the carbonic acid gas utilizing in stack gas, make sodium hydroxide generate sodium bicarbonate, sodium bicarbonate further reacts with sodium hydroxide and generates sodium carbonate, meanwhile, excessive hydrogen calcium oxide neutralization residual in filtrate is generated to precipitation of calcium carbonate; Reacted filtrate is removed by filter to the acidizing fluid that obtains being rich in Sodium Thiocyanate 99 and sodium carbonate after precipitation of calcium carbonate.
" evaporation concentration operation " by removing after calcium carbonate, the acidizing fluid concentration and evaporation that is rich in Sodium Thiocyanate 99 and sodium carbonate reduces moisture.
" crystallisation by cooling-separation circuit " is according to the dissolubility difference of sodium carbonate and Sodium Thiocyanate 99, and concentrated solution is cooled to relevant temperature, and substep is separated out crystals of sodium carbonate and Sodium Thiocyanate 99 crystal.
" freezing Steppecd crystallization " that the inventive method is partly introduced with background technology compares, and has advantages of that device is simple, operational path is shorter, and saves refrigerator system, and process cost is low, and process cost is existing methods 35% to 40%.Industrial electro depletion lacks 75% to 80%, reclaims sodium carbonate 80% to 85% from waste liquid, makes the sodium carbonate outsourcing amount in sweetening process directly reduce 65% to 70%.Existing method need to be chilled to-5 ℃ of following refrigerated waters as crystallization water coolant in addition, and the Sulfothiorine of extraction and Sodium Thiocyanate 99 product purity are low, and can not make up the sodium carbonate alkali source that desulphurization system needs.
The inventive method removes the desulfurization waste liquor of hydrogen sulfide in coal gas or other gas, HCN generation for the treatment of soda method, the method can be under normal temperature condition, by thermal degradation, oxidation, causticization, Sulfothiorine, sodium polysulphide, sodium sulfate in soda method desulfurization waste liquor are changed into calcium sulfite, sulfurated lime and calcium sulfate precipitation, extract highly purified sodium carbonate and Sodium Thiocyanate 99 simultaneously, reclaim soda and return to desulphurization system circulation, reduce the alkaline consumption of desulfurization operations.
Accompanying drawing explanation:
Fig. 1 the inventive method process flow diagram.
In figure: 1-strainer, 2-thermal degradation device, 3-causticizer, 4-carbonic acid gas acidifier, 5-heats concentration kettle, 6-the first crystallisation by cooling groove, 7-the second crystallisation by cooling groove, 8-the first strainer, 9-the second strainer, 10-the 3rd strainer, 11-the 4th strainer, 12-sodium carbonate whizzer, 13-Sodium Thiocyanate 99 whizzer, 14-acidifying liquid bath, 15-filtrate medial launder, A-stock liquid, B-calcium sulfate, C-crystallize sodium carbonate filter cake, D-Sodium Thiocyanate 99, the new gac of E-, F-pressurized air, G-decompose slag, H-calcium carbonate, I-milk of lime, J-purifying flue gas, K-carries filtrate after Sodium Thiocyanate 99, S-steam, W-water coolant, P-waste active carbon.
Embodiment:
First the inventive method is that stock liquid A puts into strainer 1 by soda method desulfurization waste liquor, the built-in coke of strainer 1 or gac or other sorbing material, stock liquid A is by entrained solid impurity in fractionation by adsorption waste liquid after coke or active carbon adsorption material at normal temperatures and pressures, strainer can operate continuously several months very several weeks, when absorption reaches capacity or can or change sorbent material by recoil during resistance increment, keep adsorber working properly.
Stock liquid A after rough purification is sent into thermal degradation device 2, with steam S, heat, making the decomposition of components such as Sulfothiorine, sodium polysulphide is S-WAT and sodium sulphite, and separate out elemental sulfur and evaporate part moisture, be blown into the S-WAT and the sodium sulphite that in pressurized air F oxidation stock liquid A, generate simultaneously, convert it into sodium sulfate.Oxidizing reaction service temperature is controlled within the scope of 85～125 ℃.When heating the decomposition of components such as Sulfothiorine, sodium polysulphide be S-WAT and sodium sulphite, and separate out elemental sulfur.
Reaction solution after thermolysis-oxidizing reaction is put into the first strainer 8 elimination impurity G, and filtrate is sent into causticizer 3, adds milk of lime I to carry out causticizing reaction, makes sodium sulfate and remaining S-WAT N
a2sO
3with sodium sulphite N
a2s changes into respectively calcium sulfate and calcium sulfite and sulfurated lime precipitation, and sodium ion reacts with hydroxide ion and generates sodium hydroxide, and causticizing reaction temperature is within the scope of 85～125 ℃.Causticizing reaction liquid is sent into the second strainer 9 and is leached calcium sulfate and calcium sulfite and sulfurated lime B, enrichment Sodium Thiocyanate 99 and sodium hydroxide in filtrate, filtrate moves into carbonic acid gas acidifier 4, be blown into purifying flue gas J simultaneously, the neutralization reaction of carbonic acid gas and sodium hydroxide occurs in acidifier, and reaction final product is sodium carbonate.Acidification reaction is removed calcium hydroxide superfluous in filtrate simultaneously and is generated precipitation of calcium carbonate and solution separating.Acidizing fluid removes by filter precipitation of calcium carbonate H through the 3rd strainer 10.Filtrate collection is to acidifying liquid bath 14.In acidizing fluid enrichment Sodium Thiocyanate 99 and sodium carbonate, as extracting product Sodium Thiocyanate 99 and reclaiming the stock liquid of sodium carbonate.So far the pre-treatment of stock liquid finishes.Acidizing fluid is moved into heating concentration kettle 5, and solution heats concentrated in still, and adds new gac E absorption to remain in the solid impurity in solution, makes solution more colourless clean.Concentrated end put into the 4th strainer 11 by concentrated solution, removes by filter impurity and takes out waste active carbon P.Concentrated solution is put into the first crystallisation by cooling groove 6 use water at low temperature (18～25 ℃) later and be cooled to specified temperature (35～45 ℃), cool slurry is separated out crystals of sodium carbonate, and slurries are put into sodium carbonate centrifugal filter 12, filters out crystallize sodium carbonate thing C.And then filtrate is put into the second crystallisation by cooling groove 7 use water at low temperature (18～25 ℃) be cooled to specified temperature (25～30 ℃), separate out object product Sodium Thiocyanate 99 crystal, slurry impouring Sodium Thiocyanate 99 whizzer 13 is filtered, take out crystalline product Sodium Thiocyanate 99 D product, filtrate collection is to filtrate medial launder 15.This is the final filtrate of the inventive method, does not contain Sulfates, only contains a small amount of sodium carbonate and Sodium Thiocyanate 99, and this class filtrate K returns to desulphurization circulating liquid system.From the isolated sodium carbonate of sodium carbonate centrifugal filter, also return to desulfurization workshop section as desulfurization alkali, regeneration sodium carbonate can partly substitute new alkali.
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| CN111484211A (en) * | 2020-06-09 | 2020-08-04 | 河南东泰制药有限公司 | Treatment method and device for high-concentration alkaline waste liquid in 2, 6-dichlorodiphenylamine production |
| CN112340911A (en) * | 2020-09-29 | 2021-02-09 | 陕西陕焦化工有限公司 | Method for recycling desulfurization waste liquid |
| CN112499813A (en) * | 2020-11-20 | 2021-03-16 | 成都千砺金科技创新有限公司 | Production method for full resource recycling of waste water in titanium dioxide production by sulfuric acid process |
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| CN115090096A (en) * | 2022-06-06 | 2022-09-23 | 武汉天源环保股份有限公司 | Landfill leachate deodorization method and system |
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