CN102259894A - Comprehensive recovery process of secondary salts from coking plant desulfurization waste liquid - Google Patents
Comprehensive recovery process of secondary salts from coking plant desulfurization waste liquid Download PDFInfo
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- CN102259894A CN102259894A CN 201110140277 CN201110140277A CN102259894A CN 102259894 A CN102259894 A CN 102259894A CN 201110140277 CN201110140277 CN 201110140277 CN 201110140277 A CN201110140277 A CN 201110140277A CN 102259894 A CN102259894 A CN 102259894A
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- ammonium
- desulfurization waste
- waste liquor
- obtains
- ammonium sulfate
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- 239000002699 waste material Substances 0.000 title claims abstract description 38
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 37
- 230000023556 desulfurization Effects 0.000 title claims abstract description 37
- 239000007788 liquid Substances 0.000 title claims abstract description 29
- 150000003839 salts Chemical group 0.000 title claims abstract description 23
- 238000004939 coking Methods 0.000 title abstract description 4
- 238000011084 recovery Methods 0.000 title abstract 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 29
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims abstract description 24
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000004061 bleaching Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 239000006200 vaporizer Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000008247 solid mixture Substances 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000003245 coal Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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Abstract
The invention belongs to the field of environmental protection and in particular discloses a comprehensive recovery process of secondary salts from a coking plant desulfurization waste liquid. The comprehensive recovery process is characterized by decolorizing the desulfurization waste liquid, evaporating and separating to obtain an ammonium sulfate and ammonium thiosulfate solid mixture and a separation liquid; and filtering the separation liquid, crystallizing, washing and drying to obtain an ammonium thiocyanate finished product. The comprehensive recovery process disclosed by the invention has the advantages that: the process is simple and clear, three secondary salts namely ammonium thiocyanate, ammonium thiosulfate and ammonium sulfate in the desulfurization waste liquid are simultaneously recovered at smaller energy consumption, the whole process is a physical processes, no other agents are introduced, secondary pollution is avoided and harmless treatment of wastewater is achieved.
Description
(1) technical field
The invention belongs to field of environment protection, particularly a kind of coke-oven plant desulfurization waste liquor secondary salt comprehensive recycling process.
(2) background technology
The coke production ability of China occupies first place in the world, and in the process of producing, has nearly 1/3 sulphur to transfer to from feed coal in the coke-oven gas that is produced, with H
2The form of S exists, and also has HCN in the coke-oven gas simultaneously, and this just need remove them before coke-oven gas uses in the lump.
The present desulfurization technology of coking industry is a lot, adopts maximum still with NH now
3HPF sulfur removal technology for alkali source.After adopting the desulfurization of this kind technology, mainly be to contain NH in the desulfurization waste liquor
4CNS, (NH
4)
2S
2O
3(NH
4)
2SO
4, these secondary salts accumulate in doctor solution, when total salt concentration reaches 300g/L, must emit a part of waste liquid, otherwise can influence the steady running of front desulphurization system, and this will produce a large amount of desulfurization waste liquors needs to handle.Throughput is 1,200,000 tons/year coal chemical enterprise, will produce about 1 ten thousand stere desulfurization waste liquor every year, according to the requirement of Environmental Protection in China, these desulfurization waste liquors are absolute prohibition dischargings, to desulfurization waste liquor be treated as coal chemical enterprise the problem that must face.
To the processing of this kind desulfurization waste liquor,, can not tackle the problem at its root if adopt the processing mode of returning coal blending.Because after the coal that has a desulfurization waste liquor enters coking furnace, at high temperature still change into sulfocompounds such as sulfurous gas and hydrogen sulfide, finally still get back in the desulfurization waste liquor, in the course of time the accumulation of the sulfide in the desulfurization waste liquor is more and more, will seriously reduce sweetening effectiveness on the one hand, cause heavy corrosion on the other hand production unit.Therefore by a kind of technology the secondary salt in this desulfurization waste liquor is reclaimed, when obtaining certain economic benefit, can thoroughly address this problem.
(3) summary of the invention
The present invention provides the coke-oven plant that a kind of technology is simple, energy consumption is low desulfurization waste liquor secondary salt comprehensive recycling process in order to remedy the deficiencies in the prior art.
The present invention is achieved through the following technical solutions:
A kind of coke-oven plant desulfurization waste liquor secondary salt comprehensive recycling process, it is characterized in that: with the decolouring of desulfurization waste liquor process, evaporation, separation, obtain ammonium thiosulfate and ammonium sulfate solids mixture and parting liquid, parting liquid after filtration, crystallization, washing, dry back obtain the ammonium thiocyanate finished product; Ammonium thiosulfate and ammonium sulfate solids mixture separation adopt the dosing dissolving, separate, the crystalline method obtains the thiosulfuric acid ammonium product, and the isolated solid of this step washs, separates with suitable quantity of water, obtains the ammonium sulfate finished product.
The present invention mainly comprises the steps:
(1) under 104 ~ 102Pa vacuum state, in desulfurization waste liquor, add the gac that accounts for waste liquid quality 1 ‰ ~ 1%, under 70 ~ 95 ℃, desulfurization waste liquor is stirred decolouring 4 ~ 10h, the waste liquid after the decolouring to be filtered, filtrate enters vaporizer;
It is preferably, and decolouring vacuum tightness is 5000 ~ 1000Pa, and the amount that adds gac is 2 of desulfurization waste liquor quality ~ 5 ‰, and bleaching temperature is 75 ~ 85 ℃.
(2) under 60 ~ 95 ℃, with filtrate vacuum-evaporation, when being concentrated into crystallization and occurring, be cooled to 50 ~ 65 ℃, separate the crystalline mixture that obtains ammonium thiosulfate and ammonium sulfate, isolated liquid is through membrane filter appts, and the filtered liquid that obtains enters the crystallization kettle crystallization;
It is preferably, and the evaporation concentration temperature of filtrate is 75 ~ 85 ℃, and the film of membrane filter appts is ceramic membrane or metallic membrane, and the aperture is 0.03 ~ 0.3 μ m, and filtration temperature is 50 ~ 60 ℃.
(3) add the ammonium thiocyanate washings that accounts for filtration liquid measure 3 ~ 10% in crystallization kettle, the control cooling rate is 1 ~ 5 ℃/h, is cooled to 10 ~ 30 ℃, obtains the ammonium thiocyanate crystallization, centrifugation ammonium thiocyanate crude product and mother liquor, and the ammonium thiocyanate crude product obtains finished product through washing;
It is preferably, and the control cooling rate is 2 ~ 3 ℃/h, is cooled to 15 ~ 25 ℃.
(4) with mother liquor and thiosulfuric acid ammonium solution preparation dosing, the mixture of ammonium thiosulfate and ammonium sulfate is dissolved down at 60 ~ 90 ℃, filtration obtains solid ammonium sulfate crude product and ammonium thiosulfate supersaturated solution, be cooled to 0 ~ 30 ℃ of crystallization, obtain the thiosulfuric acid ammonium product, the ammonium sulfate crude product that filtration obtains washes with water at normal temperatures, filters the back and obtains the ammonium sulfate finished product.
It is preferably, and the concentration range of ammonium thiosulfate is 5 ~ 25% in the dosing, and the solvent temperature of mixture is 70 ~ 80 ℃, and the decrease temperature crystalline temperature is 10 ~ 25 ℃.
Technology of the present invention is simple, clear process, can reclaim ammonium thiocyanate in the desulfurization waste liquor, ammonium thiosulfate and three kinds of secondary salts of ammonium sulfate simultaneously with less energy consumption, the sulphur that before liquid advances crystallization kettle, adopts the membrane filtration mode to remove in the evaporative process to be produced, obtained to promote the method for ammonium thiocyanate quality with less energy consumption, higher efficient, because the sulphur absolute magnitude that film is handled herein is very little, these characteristics have guaranteed the long-period stable operation of film; Adopted the process of programmed cooling in the ammonium thiocyanate crystallisation process, obtained the higher ammonium thiocyanate product of purity, whole process is a physical process, does not introduce other medicaments, has avoided secondary pollution, has realized the harmless treatment of waste water.
(4) description of drawings
The present invention is further illustrated below in conjunction with accompanying drawing.
Accompanying drawing is a process flow diagram of the present invention.
(5) embodiment
Embodiment 1:
Get coal chemical enterprise desulfurization wastewater 1000g(ammonium thiocyanate 21.35%, ammonium thiosulfate 18.75%, ammonium sulfate 1.25%), be 5000Pa at first in vacuum tightness, 75 ℃ of 5h that decolour down enter evaporating kettle with the liquid after the decolouring, 5000Pa, 80 ℃ of following evaporating off water 390 grams.Be cooled to 60 ℃, adopt whizzer to isolate ammonium thiosulfate/ammonium sulfate composite salt 148 grams; Liquid after the separation filters down at 55 ℃, filter back liquid and enter the crystallization kettle crystallization, solution 45 grams that add washing ammonium thiocyanate finished product, Tc is 25 ℃, and cooling rate is 3 ℃/h, keeps 2h under this temperature, centrifuging, washing, obtain finished product ammonium thiocyanate 162 grams, purity 97.4%, sulphur content is less than 0.05%.Isolated 148 gram ammonium thiosulfate/ammonium sulfate composite salt are added 180g dosing (160 gram mother liquor+20g5% thiosulfuric acid ammonium solution), at 75 ℃ of dissolution filters, obtain ammonium sulfate crude salt insolubles 21g and 315ml solution, with 315ml solution 20 ℃ of crystallizations, washing, obtain ammonium thiosulfate 94.2g, purity 94.5%; With 21g insolubles 3ml water dissolution, filter, obtain ammonium sulfate solids 8.2g, purity 94.7%.
Embodiment 2:
Get coal chemical enterprise desulfurization wastewater 1000g(ammonium thiocyanate 18.32%, ammonium thiosulfate 17.75%, ammonium sulfate 0.64%), be 5000Pa at first in vacuum tightness, 75 ℃ of 5h that decolour down enter evaporating kettle with the liquid after the decolouring, 5000Pa, 80 ℃ of following evaporating off water 470 grams.Be cooled to 55 ℃, adopt whizzer to isolate ammonium thiosulfate/ammonium sulfate composite salt 126 grams; Liquid after the separation filters down at 50 ℃, filter back liquid and enter the crystallization kettle crystallization, solution 35 grams that add washing ammonium thiocyanate finished product, Tc is 30 ℃, and cooling rate is 2 ℃/h, keeps 1h under this temperature, centrifuging, washing, obtain finished product ammonium thiocyanate 146 grams, purity 96.8%, sulphur content is less than 0.05%.Isolated 126 gram ammonium thiosulfate/ammonium sulfate composite salt are added 134g dosing (124 gram mother liquor+10g5% thiosulfuric acid ammonium solution), at 60 ℃ of dissolution filters, obtain ammonium sulfate crude salt insolubles 14g and 245ml solution, with 245ml solution 30 ℃ of crystallizations, washing, obtain ammonium thiosulfate 78.1g, purity 93.8%; With 14g insolubles 2.4ml water dissolution, filter, obtain ammonium sulfate solids 4.5g, purity 95.3%.
Embodiment 3:
Other are with embodiment 2, just remove the vaporised liquid after the ammonium thiosulfate, do not adopt membrane filtration before entering crystallization kettle, and ammonium thiocyanate crystallization cooling rate is 6 ℃/h.The result obtains finished product ammonium thiocyanate 132 grams, purity 95.4%, sulphur content 0.15%.
Claims (6)
1. coke-oven plant's desulfurization waste liquor secondary salt comprehensive recycling process, it is characterized in that: with the decolouring of desulfurization waste liquor process, evaporation, separation, obtain ammonium thiosulfate and ammonium sulfate solids mixture and parting liquid, parting liquid after filtration, crystallization, washing, dry back obtain the ammonium thiocyanate finished product; Ammonium thiosulfate and ammonium sulfate solids mixture separation adopt the dosing dissolving, separate, the crystalline method obtains the thiosulfuric acid ammonium product, and the isolated solid of this step washs, separates with suitable quantity of water, obtains the ammonium sulfate finished product.
2. coke-oven plant according to claim 1 desulfurization waste liquor secondary salt comprehensive recycling process is characterized by, and mainly comprises the steps:
(1) under 104 ~ 102Pa vacuum state, in desulfurization waste liquor, add the gac that accounts for waste liquid quality 1 ‰ ~ 1%, under 70 ~ 95 ℃, desulfurization waste liquor is stirred decolouring 4 ~ 10h, the waste liquid after the decolouring to be filtered, filtrate enters vaporizer;
(2) under 60 ~ 95 ℃, with filtrate vacuum-evaporation, when being concentrated into crystallization and occurring, be cooled to 50 ~ 65 ℃, separate the crystalline mixture that obtains ammonium thiosulfate and ammonium sulfate, isolated liquid is through membrane filter appts, and the filtered liquid that obtains enters the crystallization kettle crystallization;
(3) add the ammonium thiocyanate washings that accounts for filtration liquid measure 3 ~ 10% in crystallization kettle, the control cooling rate is 1 ~ 5 ℃/h, is cooled to 10 ~ 30 ℃, obtains the ammonium thiocyanate crystallization, centrifugation ammonium thiocyanate crude product and mother liquor, and the ammonium thiocyanate crude product obtains finished product through washing;
(4) with mother liquor and thiosulfuric acid ammonium solution preparation dosing, the mixture of ammonium thiosulfate and ammonium sulfate is dissolved down at 60 ~ 90 ℃, filtration obtains solid ammonium sulfate crude product and ammonium thiosulfate supersaturated solution, be cooled to 0 ~ 30 ℃ of crystallization, obtain the thiosulfuric acid ammonium product, the ammonium sulfate crude product that filtration obtains washes with water at normal temperatures, filters the back and obtains the ammonium sulfate finished product.
3. coke-oven plant according to claim 1 and 2 desulfurization waste liquor secondary salt comprehensive recycling process is characterized in that: in the step (1), decolouring vacuum tightness is 5000 ~ 1000Pa, and the amount that adds gac is 2 of desulfurization waste liquor quality ~ 5 ‰, and bleaching temperature is 75 ~ 85 ℃.
4. coke-oven plant according to claim 1 and 2 desulfurization waste liquor secondary salt comprehensive recycling process, it is characterized in that: in the step (2), the evaporation concentration temperature of filtrate is 75 ~ 85 ℃, and the film of membrane filter appts is ceramic membrane or metallic membrane, the aperture is 0.03 ~ 0.3 μ m, and filtration temperature is 50 ~ 60 ℃.
5. coke-oven plant according to claim 1 and 2 desulfurization waste liquor secondary salt comprehensive recycling process is characterized in that: in the step (3), the control cooling rate is 2 ~ 3 ℃/h, is cooled to 15 ~ 25 ℃.
6. coke-oven plant according to claim 1 and 2 desulfurization waste liquor secondary salt comprehensive recycling process, it is characterized in that: in the step (4), the concentration range of ammonium thiosulfate is 5 ~ 25% in the dosing, and the solvent temperature of mixture is 70 ~ 80 ℃, and the decrease temperature crystalline temperature is 10 ~ 25 ℃.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674398A (en) * | 2012-05-11 | 2012-09-19 | 北京旭阳化工技术研究院有限公司 | Method for recovering ammonium sulfate and ammonium thiocyanate from desulfuration waste liquor |
| CN102701510A (en) * | 2012-06-28 | 2012-10-03 | 镇江市三环环保技术咨询服务有限公司 | Alkali-added wet type oxidation catalytic desulfurization waste solution recycling method |
| CN103663497A (en) * | 2013-09-24 | 2014-03-26 | 北京艾思合众环保科技有限公司 | Method for improving whiteness of sodium thiocyanate in coking desulfurization waste liquid |
| CN103663496A (en) * | 2013-09-24 | 2014-03-26 | 北京艾思合众环保科技有限公司 | Method for improving purity of sodium thiocyanate in coking and desulfurizing waste liquid |
| CN103708501A (en) * | 2013-12-18 | 2014-04-09 | 武汉科技大学 | Method for refining coked crude ammonium sulfate through membrane crystallization |
| CN103787439A (en) * | 2014-02-26 | 2014-05-14 | 河北凯跃化工集团有限公司 | Gas wetting purification desulfurizing solution zero-emission method |
| CN106082137A (en) * | 2016-06-21 | 2016-11-09 | 山东铁雄冶金科技有限公司 | A kind of comprehensively utilize coking low-quality sulfur and the system of doctor solution secondary salt and technique |
| CN106745064A (en) * | 2016-11-23 | 2017-05-31 | 安徽工业大学 | A kind of method that ammonium thiocyanate is removed in the crude salt from ammonium sulfate |
| CN109110859A (en) * | 2018-09-11 | 2019-01-01 | 唐山中大科技有限公司 | A kind of coking desulfurization waste liquor advanced treatment process |
| CN110393975A (en) * | 2019-08-19 | 2019-11-01 | 山信软件股份有限公司 | Doctor solution proposes the control method and system of refined salt |
| CN110937611A (en) * | 2019-11-01 | 2020-03-31 | 临涣焦化股份有限公司 | System and method for improving purity of secondary salt in desulfurization waste liquid |
| CN111072047A (en) * | 2020-01-21 | 2020-04-28 | 鞍钢股份有限公司 | Method for extracting ammonium sulfate from desulfurization waste liquid |
| CN112794291A (en) * | 2021-02-26 | 2021-05-14 | 中冶焦耐(大连)工程技术有限公司 | Process and system for pretreatment of waste liquid of low-quality sulfur and auxiliary salt produced from coke oven gas desulfurization |
| CN113716778A (en) * | 2021-09-01 | 2021-11-30 | 清创人和生态工程技术有限公司 | Zero-emission treatment method for secondary salt produced by coke oven gas desulfurization waste liquid |
| CN118666437A (en) * | 2024-05-09 | 2024-09-20 | 河北协同水处理技术有限公司 | Method for treating desulfurization waste liquid |
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674398A (en) * | 2012-05-11 | 2012-09-19 | 北京旭阳化工技术研究院有限公司 | Method for recovering ammonium sulfate and ammonium thiocyanate from desulfuration waste liquor |
| CN102701510A (en) * | 2012-06-28 | 2012-10-03 | 镇江市三环环保技术咨询服务有限公司 | Alkali-added wet type oxidation catalytic desulfurization waste solution recycling method |
| CN103663497A (en) * | 2013-09-24 | 2014-03-26 | 北京艾思合众环保科技有限公司 | Method for improving whiteness of sodium thiocyanate in coking desulfurization waste liquid |
| CN103663496A (en) * | 2013-09-24 | 2014-03-26 | 北京艾思合众环保科技有限公司 | Method for improving purity of sodium thiocyanate in coking and desulfurizing waste liquid |
| CN103708501B (en) * | 2013-12-18 | 2017-08-25 | 武汉科技大学 | A kind of method that membrane crystallization refines the thick sulphur ammonium of coking |
| CN103708501A (en) * | 2013-12-18 | 2014-04-09 | 武汉科技大学 | Method for refining coked crude ammonium sulfate through membrane crystallization |
| CN103787439A (en) * | 2014-02-26 | 2014-05-14 | 河北凯跃化工集团有限公司 | Gas wetting purification desulfurizing solution zero-emission method |
| CN103787439B (en) * | 2014-02-26 | 2015-01-14 | 河北凯跃化工集团有限公司 | Gas wetting purification desulfurizing solution zero-emission method |
| CN106082137A (en) * | 2016-06-21 | 2016-11-09 | 山东铁雄冶金科技有限公司 | A kind of comprehensively utilize coking low-quality sulfur and the system of doctor solution secondary salt and technique |
| CN106082137B (en) * | 2016-06-21 | 2018-02-23 | 山东铁雄冶金科技有限公司 | A kind of system and technique for comprehensively utilizing coking low-quality sulfur and doctor solution secondary salt |
| CN106745064A (en) * | 2016-11-23 | 2017-05-31 | 安徽工业大学 | A kind of method that ammonium thiocyanate is removed in the crude salt from ammonium sulfate |
| CN109110859B (en) * | 2018-09-11 | 2021-03-23 | 唐山中大科技有限公司 | Coking desulfurization waste liquid advanced treatment process |
| CN109110859A (en) * | 2018-09-11 | 2019-01-01 | 唐山中大科技有限公司 | A kind of coking desulfurization waste liquor advanced treatment process |
| CN110393975A (en) * | 2019-08-19 | 2019-11-01 | 山信软件股份有限公司 | Doctor solution proposes the control method and system of refined salt |
| CN110393975B (en) * | 2019-08-19 | 2021-07-23 | 山信软件股份有限公司 | Control method and system for extracting refined salt from desulfurization solution |
| CN110937611A (en) * | 2019-11-01 | 2020-03-31 | 临涣焦化股份有限公司 | System and method for improving purity of secondary salt in desulfurization waste liquid |
| CN110937611B (en) * | 2019-11-01 | 2023-05-23 | 临涣焦化股份有限公司 | System and method for improving purity of secondary salt of desulfurization waste liquid |
| CN111072047A (en) * | 2020-01-21 | 2020-04-28 | 鞍钢股份有限公司 | Method for extracting ammonium sulfate from desulfurization waste liquid |
| CN111072047B (en) * | 2020-01-21 | 2022-09-16 | 鞍钢股份有限公司 | A kind of method for extracting ammonium sulfate from desulfurization waste liquid |
| CN112794291A (en) * | 2021-02-26 | 2021-05-14 | 中冶焦耐(大连)工程技术有限公司 | Process and system for pretreatment of waste liquid of low-quality sulfur and auxiliary salt produced from coke oven gas desulfurization |
| CN112794291B (en) * | 2021-02-26 | 2024-02-13 | 中冶焦耐(大连)工程技术有限公司 | Pretreatment process and system for low-quality sulfur and auxiliary salt waste liquid produced by coke oven gas desulfurization |
| CN113716778A (en) * | 2021-09-01 | 2021-11-30 | 清创人和生态工程技术有限公司 | Zero-emission treatment method for secondary salt produced by coke oven gas desulfurization waste liquid |
| CN118666437A (en) * | 2024-05-09 | 2024-09-20 | 河北协同水处理技术有限公司 | Method for treating desulfurization waste liquid |
| CN118666437B (en) * | 2024-05-09 | 2026-02-06 | 河北协同水处理技术有限公司 | Method for treating desulfurization waste liquid |
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