CN103754896B - A kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater - Google Patents
A kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater Download PDFInfo
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- CN103754896B CN103754896B CN201310716852.6A CN201310716852A CN103754896B CN 103754896 B CN103754896 B CN 103754896B CN 201310716852 A CN201310716852 A CN 201310716852A CN 103754896 B CN103754896 B CN 103754896B
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- sodium hydrosulfite
- natrii sulfas
- hydrosulfite wastewater
- oxidation
- method extracting
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- 239000002351 wastewater Substances 0.000 title claims abstract description 28
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 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 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000011593 sulfur Substances 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims description 29
- 238000007254 oxidation reaction Methods 0.000 claims description 29
- 239000012452 mother liquor Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- 238000000605 extraction Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000004280 Sodium formate Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 235000019254 sodium formate Nutrition 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater, first sulfur-containing compound in the sodium hydrosulfite wastewater after concentration is changed into sodium sulfate, is subsequently cooled to-2 DEG C, in efficient concentration separator, sodium chloride crystal precipitates out, the Natrii Sulfas content folding Na of extraction2SO4?% is 40%.
Description
Technical field
The invention mainly relates to field of waste water treatment, be specifically related to a kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater.
Background technology
Sodium formate method sodium hydrosulfite production technology is China or even main flow sodium hydrosulfite production method in the world, has the advantages such as advanced technology, production efficiency are high. But in production process, produced thickened waste water constituent is complicated, COD value is high, mainly containing multiple salt and the Organic substances such as mercaptoethanol, ethylene glycol such as sodium formate, sodium sulfite, sodium sulfate, sodium thiosulfate, bunte saltses, and is difficult to biochemical degradation. The processing modes such as the burning that industry is commonly used, not only equipment investment is big and processing cost is more than 200 yuan/ton, thus becoming sodium hydrosulfite enterprise expansion production scale, reducing the major technology bottleneck that generation cost is encountered. The present invention develops the oxidation and denitration technique concentrating waste water for sodium hydrosulfite. The content studied still belongs to the first time at home, therefore the research not only can fill up the market competitiveness of the technological gap of domestic relevant industries, improving product, turn waste into wealth, also energy-conservation, reduce discharging while realize recycling of raw material, wide market, economic and social benefit are huge.
Summary of the invention
The present invention provides a kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater, and the sulfur-containing compound in waste water is transformed into Natrii Sulfas and extracts by utilization.
The present invention is achieved by the following technical solutions:
A kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater, comprises the following steps:
(1) first the sodium hydrosulfite wastewater after concentration is joined in catalytic oxidation unit, utilize the oxidants such as ozone to carry out catalytic oxidation, the selective oxidation of sulfur containing compounds in particular in sodium hydrosulfite wastewater is become the oxidation solution rich in sodium sulfate;
(2) oxidation solution obtained above is entered freezing denitration unit,-5 DEG C of chilled-water systems are adopted to cool down, subsequently into crystallization in efficient concentration separator, settle down in decanting zone, magma is from flowing to centrifuge, being centrifugally separating to obtain solid product sal glauberi, centrifuge mother liquor enters circulating mother liquor groove and is pumped back to catalytic oxidation unit circulation by circulating mother liquor.
A kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater, described sodium hydrosulfite wastewater is a kind of waste water containing one or more mixing cpds in sodium formate, sodium sulfite, bunte salts, mercaptoethanol, ethylene glycol etc.
A kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater, described freezing denitration unit cools down for-5 DEG C of chilled-water systems of employing, the method for Crystallization Separation in efficient concentration separator.
A kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater, described oxidation solution is alkalescence, and pH is 9-10.
A kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater, in described freezing denitration unit, efficient concentration separator control temperature is-2 DEG C
The invention have the advantage that
The present invention is extracted value product from sodium hydrosulfite wastewater, turns waste into wealth, and has the good value of environmental protection; The Natrii Sulfas content that the present invention produces is high, and crystal color is water white transparency.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
Embodiment 1
Waste water first uses sulfur dioxide tone pitch to pH=9～10, enters catalytic oxidation unit, and oxidizing with ozone, hydrogen peroxide, chlorine dioxide etc., the time of staying is 7～8 hours oxidation solution colors is faint yellow.
Oxidation solution is delivered to the precooler of freezing unit and carries out heat exchange with circulating mother liquor by oxidation solution delivery pump, while having reclaimed circulating mother liquor cold, oxidation solution is cooled to～18 DEG C after enter efficient concentration separator, oxidation solution in efficient concentration separator by freeze cycle pump in tubular heat exchanger with-5 DEG C of chilled water indirect heat exchange circulation temperature lowerings, efficient concentration separator controls temperature and is-2 DEG C, Natrii Sulfas is crystallization in efficient concentration separator, settle down in decanting zone, magma flow to centrifuge, it is centrifugally separating to obtain solid product sal glauberi (Natrii Sulfas), centrifuge mother liquor enters after circulating mother liquor groove is pumped to precooler and oxidation solution heat exchange by circulating mother liquor and returns catalytic oxidation unit circulation.
By the method for freezing and crystallizing, can by Na2SO4Extract from waste water with mirabilite hydrate form. Sodium sulfate belongs to heat-sensitive substance, and its saturation solubility alters a great deal with the difference of temperature, and is constantly in unsaturated state in oxidation solution, therefore, can pass through to lower the temperature, make sodium sulfate crystallize out with the form with ten water of crystallization, it is achieved sodium sulfate separates with oxidation solution. Na2SO4By Crystallization Separation, remove Na with sal glauberi form2SO4, obtain low nitre oxidation solution. Heat exchanger adopts tubular heat exchanger, makes rich nitre oxidation solution cryogenic temperature more stable, and the turnover temperature difference controls within the specific limits, and tubular heat exchanger is not easy crystallization, it is easy to field control, and heat exchanger is easy to clean. Centrifugal separation system adopts push-type centrifuge that the oxidation solution containing nitre is easily separated, and obtains sal glauberi. Owing to push-type centrifuge is continuous operations equipment, separate aperture relatively big, containing being with a large amount of tiny sodium sulphate particle in centrifuge mother liquor, be provided with mother liquor recovery system and this liquid is returned in system, as new crystal seed.
The Natrii Sulfas content folding Na that the present invention extracts2SO4% is 40%(mass ratio).
Claims (3)
1. the method extracting Natrii Sulfas in sodium hydrosulfite wastewater, it is characterised in that comprise the following steps:
(1) first the sodium hydrosulfite wastewater after concentration is joined in catalytic oxidation unit, utilize ozone oxidation agent to carry out catalytic oxidation, the selective oxidation of sulfur containing compounds in particular in sodium hydrosulfite wastewater is become the oxidation solution rich in sodium sulfate;
(2) oxidation solution obtained above is entered freezing denitration unit,-5 DEG C of chilled-water systems are adopted to cool down, subsequently into crystallization in efficient concentration separator, settle down in decanting zone, magma is from flowing to centrifuge, being centrifugally separating to obtain solid product sal glauberi, centrifuge mother liquor enters circulating mother liquor groove and is pumped back to catalytic oxidation unit circulation by circulating mother liquor; Described sodium hydrosulfite wastewater is a kind of waste water containing one or more mixing cpds in bunte salts, mercaptoethanol, ethylene glycol.
2. a kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater according to claim 1, it is characterised in that described oxidation solution is alkalescence, and pH is 9-10.
3. a kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater according to claim 1, it is characterised in that in described freezing denitration unit, efficient concentration separator control temperature is-2 DEG C.
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| CN201310716852.6A CN103754896B (en) | 2013-12-21 | 2013-12-21 | A kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104803525B (en) * | 2014-12-10 | 2017-01-11 | 青岛和合汇途工程技术有限公司 | Method for processing high salinity wastewater and device thereof |
| CN105016312B (en) * | 2015-07-08 | 2017-03-01 | 湖南龙盛环保有限公司 | A kind of method that in sodium hydrosulfite production, sulfur containing waste material recycles |
| CN109607654A (en) * | 2019-01-31 | 2019-04-12 | 内蒙古科技大学 | Device, method and the application of strong brine low temperature crystallization desalination |
| CN109665547A (en) * | 2019-02-28 | 2019-04-23 | 仲恺农业工程学院 | Method for inducing precipitation of sodium sulfate crystals in high-salinity wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3718732A (en) * | 1971-01-13 | 1973-02-27 | Virginia Chemicals Inc | Method of recovering chemical values from a formate-sodium hydrosulfite reaction mixture |
| CN1040012A (en) * | 1989-04-18 | 1990-02-28 | 老河口市石油化工总厂 | The recovery method of the processing of vat powder waste liquid and S-WAT and sodium-chlor |
| CN102050471A (en) * | 2010-11-05 | 2011-05-11 | 烟台大学 | Method for recycling sodium formate and sodium sulfite from waste sodium hydrosulfite liquid with sodium formate method |
-
2013
- 2013-12-21 CN CN201310716852.6A patent/CN103754896B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3718732A (en) * | 1971-01-13 | 1973-02-27 | Virginia Chemicals Inc | Method of recovering chemical values from a formate-sodium hydrosulfite reaction mixture |
| CN1040012A (en) * | 1989-04-18 | 1990-02-28 | 老河口市石油化工总厂 | The recovery method of the processing of vat powder waste liquid and S-WAT and sodium-chlor |
| CN102050471A (en) * | 2010-11-05 | 2011-05-11 | 烟台大学 | Method for recycling sodium formate and sodium sulfite from waste sodium hydrosulfite liquid with sodium formate method |
Non-Patent Citations (1)
| Title |
|---|
| 浅谈我厂卤水制碱冷冻脱硝工业化装置;杨佐良等;《氯碱工业》;19981031(第10期);正文第12页右栏最后一段，第13页1.2节和图2 * |
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Application publication date: 20140430 Assignee: Anhui Xingtai Financial Leasing Co.,Ltd. Assignor: GNSG ANHUI HONG SIFANG Co.,Ltd. Contract record no.: X2021340000008 Denomination of invention: A method of extracting mirabilite from sodium hydrosulfite wastewater Granted publication date: 20160615 License type: Exclusive License Record date: 20210518 |
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Denomination of invention: A method of extracting mirabilite from sodium hydrosulfite wastewater Effective date of registration: 20210527 Granted publication date: 20160615 Pledgee: Anhui Xingtai Financial Leasing Co.,Ltd. Pledgor: GNSG ANHUI HONG SIFANG Co.,Ltd. Registration number: Y2021980004042 |
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Assignee: Anhui Xingtai Financial Leasing Co.,Ltd. Assignor: GNSG ANHUI HONG SIFANG Co.,Ltd. Contract record no.: X2021340000008 Date of cancellation: 20240827 |
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