CN105130085B - A kind for the treatment of technique of coking desulfurization liquid waste and equipment - Google Patents
A kind for the treatment of technique of coking desulfurization liquid waste and equipment Download PDFInfo
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- CN105130085B CN105130085B CN201510625750.2A CN201510625750A CN105130085B CN 105130085 B CN105130085 B CN 105130085B CN 201510625750 A CN201510625750 A CN 201510625750A CN 105130085 B CN105130085 B CN 105130085B
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- storage tank
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- decolouring
- oxidation solution
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a kind for the treatment of technique of coking desulfurization liquid waste and equipment, it is related to field of desulfurization waste liquid treatment technology.A kind for the treatment of technique of coking desulfurization liquid waste, step are：Desulfurization waste liquor after the catalysis oxidation of catalyst, delivers to centrifuge to remove elemental sulfur caused by oxidizing process in stills for air blowing, and filtrate adds flocculant under agitation, while is settled 24 hours after adjusting oxidation solution pH value so that elemental sulfur and Fe in oxidation solution2+With OH in solution‑Fe caused by reaction（OH）2Colloid flocculates completely, and supernatant passes through film filter, to remove the elemental sulfur and Fe of flocculation（OH）2Colloidal impurity, then through the activated carbon decolorizing in decolouring kettle, filter processing is sent into, liquid enters evaporating kettle and is evaporated crystallization with crystallization kettle, and the ammonium sulfate and ammonium thiocyanate product of high-purity is made.Production cost of the present invention is low, easily operated, saves, be stable, while being remarkably improved the purity of product.
Description
Technical field
The present invention relates to field of desulfurization waste liquid treatment technology, and in particular to a kind of to produce high-purity sulphur with coking desulfurization waste liquor
The treatment technique of coking desulfurization liquid waste and equipment of sour ammonium and ammonium thiocyanate.
Background technology
At present, in the technique of domestic processing coking desulfurization waste liquor, traditional salt extraction technique is：Material enters single stills for air blowing
It is interior, temperature increasing catalyst oxidation so that ATS (Ammonium thiosulphate) is oxidized to ammonium sulfate, while accessory substance is elemental sulfur；Aoxidize obtained oxidation
Liquid first passes through centrifuge, filters elemental sulfur；Obtained filtrate enters decolouring kettle by centrifugal pump again and adds activated carbon progress
Decolourize, the solution after decolouring makes decolouring clear liquid be separated with activated carbon by flame filter press；Clear liquid after decolouring directly enters
Enter evaporating kettle and crystallization kettle is evaporated crystallization and obtains ammonium sulfate and ammonium thiocyanate product.
To be directly entered bleaching workshop section after desulfurization liquid oxidation, the technique has the following disadvantages i.e. traditional salt extraction technique：（1）Oxygen
Though solution filters by centrifuge after changing liquid filtering, still containing oxidation generation it is tiny, fail the list that is filtered out by centrifuge
The impurity such as matter sulfur granules, ferric iron, chloride, the purity of subsequent product will be influenceed so that product purity is extremely difficult to national mark
It is accurate；（2）Though oxidation solution filtering after solution filtered by centrifuge, still containing oxidation generation it is trickle, fail by centrifuge mistake
The simple substance sulphur granule filtered, these simple substance sulphur granules after being filtered due to oxidation are tiny, and sulphur foam can be formed in decolorization
Float on decolouring kettle upper end and be adsorbed in activated carbon surface so that the decoloring ability of activated carbon is greatly reduced, and processed in units amount disappears
The amounts of activated carbon increase of consumption；（3）Solution after oxidation filtering still contains Fe2+It is ion stabilized to exist in solution, this material
In the presence of the product purity that will all influence ammonium sulfate, ammonium thiocyanate and sodium sulfocyanate so that product purity can not be up to state standards.
In order to solve drawbacks described above existing for prior art, applicant have developed a kind of for handling coking desulfurization waste liquor
The membrane filtration that flocculates produces the Processes and apparatus of high-purity sulfuric acid ammonium and ammonium thiocyanate.
The content of the invention
It is an object of the invention to provide a kind for the treatment of technique of coking desulfurization liquid waste.
It is a further object to provide a kind of coking desulfurization waste liquor processing equipment.
The present invention is achieved by the following technical solutions：
A kind for the treatment of technique of coking desulfurization liquid waste, step are：
（1）Desulfurization waste liquor after the catalysis oxidation of catalyst, delivers to centrifuge progress in stills for air blowing after oxidation solution cooling
To remove elemental sulfur caused by oxidizing process, filtrate inputs oxidation solution storage tank for centrifugal filtration；
（2）Flocculant is added into oxidation solution storage tank under agitation, while it is small to adjust sedimentation 24 after oxidation solution pH value
When, the elemental sulfur and Fe caused in oxidation solution is acted on using adsorption-flocculation2+With OH in solution-Fe caused by reaction（OH）2Colloid
Flocculation completely, and tank bottom is fallen to, supernatant is by being transported to adjustment liquid storage tank；
（3）Supernatant is inputted into ceramic membrane filter device, to remove the elemental sulfur and Fe of flocculation（OH）2Colloidal impurity, so
The liquid after filtering is inputted into decolouring kettle again afterwards；
（4）For liquid in decolouring kettle after activated carbon decolorizing, being sent into filter makes decolouring clear liquid be separated with activated carbon,
Clear liquid after decolouring is directly entered evaporating kettle and is evaporated crystallization with crystallization kettle, and ammonium sulfate and the ammonium thiocyanate production of high-purity is made
Product.
A kind of equipment for completing treatment technique of coking desulfurization liquid waste, including be sequentially connected by pipeline original fluid container,
Stills for air blowing, centrifuge, oxidation solution storage tank, adjustment liquid storage tank, film filter, oxidation clear liquid storage tank, decolouring kettle, plate-frame filtering
Machine, decolouring clear liquid storage tank, evaporating kettle, sulphur ammonium centrifuge, ammonium thiocyanate mother liquor storage tank, crystallization kettle, ammonium thiocyanate centrifuge, lean solution
Storage tank；Wherein described oxidation solution storage tank is provided with agitating device；Spiral shell is installed between described decolouring kettle and flame filter press
Bar pump.
Further, described film filter is ceramic membrane filter device.
The present invention utilizes flocculant and regulation solution pH value so that elemental sulfur and Fe in oxidation solution2+With OH in solution-Instead
Should caused Fe（OH）2Colloid flocculates, and recycles ceramic membrane filter device to reach and removes elemental sulfur and Fe2+Deng impurity；To solve
Elemental sulfur caused by the existing oxidation of prior art filters not thorough and Fe2+Ion is existed in solution so that production is consumed
Amounts of activated carbon it is big, and product purity is not high, the problem of being extremely difficult to national standard.
During operation, desulfurization waste liquor enters stills for air blowing by original fluid container by stills for air blowing feed pump, and stills for air blowing are built with a certain amount of
Catalyst, centrifuge is delivered to after the oxidation solution cooling after the completion of oxidation, and to carry out centrifugal filtration single to remove caused by oxidizing process
Matter sulphur；Filtrate enters oxidation liquid storage tank, then adds a certain amount of flocculant into oxidation solution storage tank while stirring, adjusts simultaneously
Oxidation solution pH value, the oxidation solution standing sedimentation after adjustment 24 hours, the elemental sulfur caused in oxidation solution is acted on using adsorption-flocculation
And Fe2+With OH in solution-Fe caused by reaction（OH）2Colloid flocculates and falls to tank bottom completely, and supernatant passes through conveying
Pump enters adjustment liquid storage tank；Oxidation solution after adjustment enters ceramic membrane filter device by ceramic membrane feed pump, to remove flocculation
Elemental sulfur and Fe（OH）2The impurity such as colloid, the liquid after filtering is then delivered into decolouring kettle by oxidation clear liquid storage tank again, adds and lives
Property charcoal is decolourized, and the solution after decolouring is pumped to flame filter press by screw rod makes decolouring clear liquid be separated with activated carbon；It is de-
Clear liquid after color is directly entered the ammonium sulfate for obtaining high-purity and the ammonium thiocyanate production that evaporating kettle is evaporated crystallization with crystallization kettle
Product.
Compared with prior art, the invention has the advantages that：
（1）Acted on using the adsorption-flocculation of flocculant, while adjust oxidation solution pH value so that not by centrifuge in oxidation solution
The tiny simple substance sulphur granule and Fe filtered out2+With OH in solution-Fe caused by reaction（OH）2Colloid sedimentation flocculation；
(2) flocculating setting thing is removed by ceramic membrane filter caused by, to reduce elemental sulfur and Fe in oxidation solution2+'s
Content, reduces the consumption of follow-up bleaching workshop section activated carbon, while greatly reduces the impurity content in solution；
（3）Oxidation solution filters off the impurity of small particle, it is pure to improve subsequent evaporation crystallized liquid by ceramic membrane filter device
Degree, obtains the ammonium sulfate, ammonium thiocyanate and ammonium sulfate product of high-purity；
（4）The steam consumption of desulfurization waste liquor per ton is down to 0.8t, the activated carbon of desulfurization waste liquor per ton by 1.5t before
Consumption is down to 1.5kg by 4kg, reduces production cost.
In summary, it is easily operated present invention reduces production cost, there is energy-conservation, stable, while can
Significantly improve the purity of product.
Brief description of the drawings
Fig. 1 is the structural representation of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
A kind of equipment for completing treatment technique of coking desulfurization liquid waste as shown in Figure 1, including connected successively by pipeline
Original fluid container 1, stills for air blowing 3, centrifuge 4, oxidation solution storage tank 5, adjustment liquid storage tank 7, film filter 9, the oxidation clear liquid storage tank connect
10th, decolouring kettle 12, flame filter press 14, decolouring clear liquid storage tank 15, evaporating kettle 17, sulphur ammonium centrifuge 18, the storage of ammonium thiocyanate mother liquor
Groove 19, crystallization kettle 20, ammonium thiocyanate centrifuge 21, lean solution storage tank 22；Wherein described oxidation solution storage tank 5 is provided with stirring dress
Put；Screw pump 13 is installed between described decolouring kettle 12 and flame filter press 14.
During operation, desulfurization waste liquor enters stills for air blowing 3 by original fluid container 1 by stills for air blowing feed pump 2, and stills for air blowing 3 are built with one
Quantitative catalyst, centrifuge 4 is delivered to after the oxidation solution cooling after the completion of oxidation and carries out centrifugal filtration to remove oxidizing process production
Raw elemental sulfur；Filtrate enters oxidation liquid storage tank 5, then adds a certain amount of flocculant into oxidation solution storage tank while stirring,
Oxidation solution pH value is adjusted simultaneously, the oxidation solution standing sedimentation after adjustment 24 hours, is acted on and caused in oxidation solution using adsorption-flocculation
Elemental sulfur and Fe2+With OH in solution-Fe caused by reaction（OH）2Colloid flocculates and falls to tank bottom, supernatant completely
Adjustment liquid storage tank 7 is entered by delivery pump 6；Oxidation solution after adjustment enters film filter 9 by ceramic membrane feed pump 8（Ceramics
Film filter）, to remove the elemental sulfur and Fe of flocculation（OH）2The impurity such as colloid, then again by the liquid after filtering by aoxidizing
Clear liquid storage tank 10 delivers to decolouring kettle 12 by decolouring kettle feed pump 11, adds activated carbon and is decolourized, the solution after decolouring is by spiral shell
Bar pump 13, which delivers to flame filter press 14, makes decolouring clear liquid be separated with activated carbon；Liquid after decolouring immerses decolouring clear liquid storage tank
15, evaporating kettle 17 is then entered by evaporating kettle liquid-feeding pump 16, then after sulphur ammonium centrifuge, solution is sent into thiocyanic acid
Ammonium mother liquor storage tank 19, then obtain the sulphur of high-purity by what crystallization kettle 20, ammonium thiocyanate centrifuge 21 were evaporated crystallization successively
Sour ammonium and ammonium thiocyanate product, liquid are sent into lean solution storage tank 22.
Claims (2)
1. a kind for the treatment of technique of coking desulfurization liquid waste, it is characterised in that step is：
Desulfurization waste liquor delivers to centrifuge after the catalysis oxidation of catalyst, after oxidation solution cooling in stills for air blowing and carries out centrifugal filtration
To remove elemental sulfur caused by oxidizing process, filtrate input oxidation solution storage tank；
Flocculant is added into oxidation solution storage tank under agitation, while is settled 24 hours after adjusting oxidation solution pH value, is utilized
Adsorption-flocculation acts on the elemental sulfur and Fe caused in oxidation solution2+With OH in solution-Fe caused by reaction（OH）2Colloid is wadded a quilt with cotton completely
It is solidifying, and oxidation solution reservoir bottom is fallen to, supernatant is by being transported to adjustment liquid storage tank；
Supernatant is inputted into ceramic membrane filter device, to remove the elemental sulfur and Fe of flocculation（OH）2Colloidal impurity, then incited somebody to action again
Liquid input decolouring kettle after filter；
Liquid is in decolouring kettle after activated carbon decolorizing, and being sent into filter makes decolouring clear liquid be separated with activated carbon, after decolouring
Clear liquid be directly entered evaporating kettle and crystallization kettle and be evaporated crystallization, the ammonium sulfate and ammonium thiocyanate product of obtained high-purity.
2. a kind of coking desulfurization waste liquor processing equipment for being used to complete the technique described in claim 1, it is characterised in that including logical
Cross the original fluid container that pipeline is sequentially connected（1）, stills for air blowing（3）, centrifuge（4）, oxidation solution storage tank（5）, adjustment liquid storage tank（7）, pottery
Porcelain film filter（9）, oxidation clear liquid storage tank（10）, decolouring kettle（12）, flame filter press（14）, decolouring clear liquid storage tank（15）、
Evaporating kettle（17）, sulphur ammonium centrifuge（18）, ammonium thiocyanate mother liquor storage tank（19）, crystallization kettle（20）, ammonium thiocyanate centrifuge（21）、
Lean solution storage tank（22）；Wherein described oxidation solution storage tank（5）Agitating device is installed；Described decolouring kettle（12）With plate-frame filtering
Machine（14）Between screw pump is installed（13）.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510625750.2A CN105130085B (en) | 2015-09-28 | 2015-09-28 | A kind for the treatment of technique of coking desulfurization liquid waste and equipment |
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| CN201510625750.2A CN105130085B (en) | 2015-09-28 | 2015-09-28 | A kind for the treatment of technique of coking desulfurization liquid waste and equipment |
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| CN105130085B true CN105130085B (en) | 2017-12-01 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105776400B (en) * | 2016-03-09 | 2018-10-30 | 北京富海天环保科技有限公司 | It is a kind of ensure coking desulfurization waste liquor salt extraction during decolorizing efficiency device and method |
| CN108911041B (en) * | 2018-07-24 | 2021-06-29 | 江西庞泰环保股份有限公司 | Desulfurization waste liquid purifier |
| CN110510778B (en) * | 2019-09-10 | 2020-08-25 | 厦门嘉戎技术股份有限公司 | Landfill leachate pretreatment method and device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10263558A (en) * | 1997-03-26 | 1998-10-06 | Japan Organo Co Ltd | Treatment of fluorine-containing desulfurized waste water |
| WO2010150424A1 (en) * | 2009-06-26 | 2010-12-29 | 三菱重工業株式会社 | Flue-gas desulfurization system using river water and method of removing humus |
| CN102976361A (en) * | 2012-12-10 | 2013-03-20 | 北京旭阳化工技术研究院有限公司 | Method for extracting high-purity ammonium thiocyanate and ammonium sulphate from coking desulfurization/decyanation waste liquor |
| 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 |
| CN104150669A (en) * | 2014-08-22 | 2014-11-19 | 国家电网公司 | Thermal power plant desulphurization wastewater purification system and purification method |
| CN104773885A (en) * | 2015-03-26 | 2015-07-15 | 潍坊特钢集团有限公司 | Comprehensive treatment method of coking desulfurization waste liquid |
-
2015
- 2015-09-28 CN CN201510625750.2A patent/CN105130085B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10263558A (en) * | 1997-03-26 | 1998-10-06 | Japan Organo Co Ltd | Treatment of fluorine-containing desulfurized waste water |
| WO2010150424A1 (en) * | 2009-06-26 | 2010-12-29 | 三菱重工業株式会社 | Flue-gas desulfurization system using river water and method of removing humus |
| CN102976361A (en) * | 2012-12-10 | 2013-03-20 | 北京旭阳化工技术研究院有限公司 | Method for extracting high-purity ammonium thiocyanate and ammonium sulphate from coking desulfurization/decyanation waste liquor |
| 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 |
| CN104150669A (en) * | 2014-08-22 | 2014-11-19 | 国家电网公司 | Thermal power plant desulphurization wastewater purification system and purification method |
| CN104773885A (en) * | 2015-03-26 | 2015-07-15 | 潍坊特钢集团有限公司 | Comprehensive treatment method of coking desulfurization waste liquid |
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Address after: 043400 South Jin and North Han Road, Xining Village, Quwo County, Linfen City, Shanxi Province Patentee after: Shanxi Changlin Energy Technology Co Ltd Address before: 043400 50 meters north of South Jin Han Road, Xining Village, Quwo County, Linfen City, Shanxi Province Patentee before: SHANXI CHANGLIN ENVIRONMENTAL MACHINERY CO., LTD. |