CN102992469B - Method for treating sodium sulfide waste water - Google Patents
Method for treating sodium sulfide waste water Download PDFInfo
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- CN102992469B CN102992469B CN201210521764.6A CN201210521764A CN102992469B CN 102992469 B CN102992469 B CN 102992469B CN 201210521764 A CN201210521764 A CN 201210521764A CN 102992469 B CN102992469 B CN 102992469B
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Abstract
The invention relates to a method for treating sodium sulfide waste water, which comprises the following steps: mixing the sodium sulfide waste water, industrial waste sulphur and a catalyst; then introducing air for oxidation reaction; after the oxidation reaction is completed, filtering, and carrying out concentration, temperature reduction and crystallization on the filter liquor, and filtering again to obtain a sodium thiosulfate crystal and crystallizing mother liquor; and drying the sodium thiosulfate crystal to obtain sodium thiosulfate pentahydrate. The method disclosed by the invention reduces the production and operation cost by carrying out the oxidation reaction at lower temperature and pressure, thereby greatly enhancing the safety of the reaction process; the method greatly reduces the cost by using the air as an oxidation source, obtains a single product with the content of more than 98.5% after reaction, has the advantages of certain economic benefit, perpetual recycling of circulating mother liquor, zero discharge of waste liquor and is a green process.
Description
Technical field
The present invention relates to technical field of waste water processing, particularly a kind of method of processing Sodium Sulphide waste water.
Background technology
Sodium sulphite is very useful chemical, is widely used in the industries such as process hides, pharmacy, petrochemical industry.But because it has serious pollution to environment, affected it and further used.Mass-producing treatment process mainly contains 1 both at home and abroad at present) acidization absorption method, 2) precipitator method, 3) oxidation style and 4) absorption method and 5) biochemical treatment process etc.Although this several method can be processed, shortcoming is also fairly obvious.See the following form:
The hydrogen sulfide tail gas producing in Chemical Manufacture at present adopts liquid caustic soda to absorb conventionally, must cause the Sodium Sulphide waste water that a large amount of concentration is higher to produce, this waste water mainly contains sodium sulphite, sodium sulphite concentration in some waste water has approached state of saturation, in employing, the processing scheme shown in table all can not effectively be processed, and cost is huge, waste time and energy.Therefore develop an economically feasible, easy to operate, it is very necessary processing operational path completely.
Summary of the invention
For there being above problem in prior art, for there is above problem in prior art, the invention provides a kind of production technique reasonable, simple to operate and can suitability for industrialized production, the processing of non-wastewater discharge, environmental protection is from low concentration to the method that approaches the Sodium Sulphide waste water of saturation concentration.
Its technical scheme comprises the following steps:
By Sodium Sulphide waste water, industrial waste sulfur and catalyst mix, then pass into air and carry out oxidizing reaction 5-15 hour under 50-70 ℃ and 0.1-0.4Mpa pressure; Described high density Sodium Sulphide waste water, the mass ratio of catalyzer are 1:0.00045-0.00055, and described catalyzer is the one or any several mixture in aluminium sesquioxide, ferrous ammonium sulphate, Z 250, flyash, gac, ferrous sulfate, manganous sulfate, neutralized verdigris; Described Sodium Sulphide waste water and industrial waste sulfur consumption should meet: make the sodium sulphur mol ratio of oxidizing reaction be controlled at 1:1, Sodium Sulphide waste water and industrial waste sulfur pure after, the amount of substance of sodium element is 1:1 with the ratio of the amount of substance of element sulphur.
2) oxidizing reaction complete after filtration, decrease temperature crystalline after filtrate is concentrated, then obtain after filtering thiosulfuric acid sodium crystal and crystalline mother solution, thiosulfuric acid sodium crystal drying obtains five water Sulfothiorine.
Equation 1 below) be the oxidation scheme that tradition adopts, this scheme, owing to there being the generation of sodium hydroxide, cannot obtain simple Sulfothiorine, needs otherwise processed subsequent products after having reacted, therefore economy is not good enough.
We adopt equation 2) shown in production technique, first add the industrial waste sulfur appropriate with the same technique by-product of Sodium Sulphide, regulate sodium sulphur ratio, and then use air to be oxidized, can access single Sulfothiorine, aftertreatment is complete, easy, economy improves greatly simultaneously.
Such scheme can further be improved to:
In Sodium Sulphide waste water in described step 1), sodium sulphite mass concentration is 10%-40%, content requirement >=95% of industrial waste sulfur.
Crystalline mother solution in described step (2) returns in step 1 and carries out recycled with the waste water newly adding.
Described step 2) in, oxidizing reaction is filtered into heat filtering after completing, and filtrate is decrease temperature crystalline be concentrated into volume minimizing 1/3 under 60-90 degree-0.08--0.09MPa vacuum condition after.
Described step 2) in, the temperature of decrease temperature crystalline is 10-40 degree, and best Tc is at 16-24 degree.
If described catalyzer is the mixture of two kinds wherein, the mass ratio of the two is 1:2, such as described catalyzer is the mixture of aluminium sesquioxide and manganous sulfate, or the mixture of gac and ferrous sulfate.
By the technical program, the beneficial effect of obtaining is: 1) under lower temperature and pressure, carry out oxidizing reaction, reduced production and operation cost, the security of reaction process improves greatly; 2) use air as oxidation source, cost reduces greatly; 3) after reaction, obtain single product, and content is greater than 98.5%, there is certain economic benefit.4) circulating mother liquor can recycle always, and Zero discharge is a kind of friendly process.
Embodiment
Embodiment 1
In 5000L reactor, add high density Sodium Sulphide waste water 3500kg(39%), industrial waste sulfur 589kg(95%), ferrous ammonium sulphate 1.7kg, starts to stir, and is warming up to 50 ℃, starts to pass into air, controls temperature of reaction 50
oc, reaction pressure is at 0.3MPa, after 12 hours, react complete, heat filtering after completion of the reaction, solid catalyst after filtration drops into recycled in reactor after collecting again, filtrate is squeezed in concentration kettle, after being concentrated into volume and reducing 1/3, is decrease temperature crystalline under 60-90 degree-0.08--0.09MPa vacuum condition, and the temperature of decrease temperature crystalline is 16-24 degree; Finally by obtaining five water Sulfothiorine 2100kg, content 98.89% after filtration drying.
Filter gained catalyst residue and mother liquor and in 10 reaction cycle, reuse in the back, do not need any processing, on average can obtain product 2100.36kg, five water sodium thiosulfate contents 98.76%.
Embodiment 2
In 5000L reactor, add high density Sodium Sulphide waste water 3600(36%) kg, industrial waste sulfur 560kg(95%), composite catalyst (aluminium sesquioxide: manganous sulfate=1:2) 1.8kg, start to stir, be warming up to 70 ℃, start to pass into air, control temperature of reaction 70
oc, reaction pressure is at 0.1MPa, after 6 hours, react complete, heat filtering after completion of the reaction, solid catalyst after filtration drops into recycled in reactor after collecting again, filtrate is squeezed in concentration kettle, after being concentrated into volume and reducing 1/3, is decrease temperature crystalline under 60-90 degree-0.08--0.09MPa vacuum condition, and the temperature of decrease temperature crystalline is 10-15 degree; After being dried after filtration, obtain five water Sulfothiorine 2122kg, content 98.86%.
Embodiment 3
In 5000L reactor, add high density Sodium Sulphide waste water 3500kg (35%), industrial waste sulfur 529kg (95%), flyash 1.6kg, starts to stir, and is warming up to 50 ℃, starts to pass into air, controls temperature of reaction 50
oc, reaction pressure is at 0.4MPa, after 10 hours, react complete, heat filtering, drops into recycled in reactor after the solid catalyst collection after filtration again after completion of the reaction, and filtrate is squeezed in concentration kettle, after being concentrated into volume reducing 1/3 under 60-90 degree-0.08--0.09MPa vacuum condition, it is decrease temperature crystalline, the temperature of decrease temperature crystalline is 30-40 degree, finally by obtaining five water Sulfothiorine 2087kg, content 98.65% after filtration drying.
Embodiment 4
In 5000L reactor, add high density Sodium Sulphide waste water 3500 (38%) kg, industrial waste sulfur 574kg (95%), composite catalyst (gac: ferrous sulfate=1:2) 1.7kg, start to stir, be warming up to 60 ℃, start to pass into air, control temperature of reaction 60
oc, reaction pressure is at 0.2MPa, after 15 hours, react complete, heat filtering, drops into recycled in reactor after the solid catalyst collection after filtration again after completion of the reaction, and filtrate is squeezed in concentration kettle, after being concentrated into volume reducing 1/3 under 60-90 degree-0.08--0.09MPa vacuum condition, it is decrease temperature crystalline, the temperature of decrease temperature crystalline is 20-30 degree, finally by obtaining five water Sulfothiorine 2045kg, content 98.80% after filtration drying.
Embodiment 5
In 5000L reactor, add high density Sodium Sulphide waste water 3800kg (38%), industrial waste sulfur 624kg(95%), Z 250 2kg, starts to stir, and is warming up to 70 ℃, starts to pass into air, controls temperature of reaction 70
oc, reaction pressure is at 0.1MPa, after 8 hours, react complete, heat filtering, drops into recycled in reactor after the solid catalyst collection after filtration again after completion of the reaction, and filtrate is squeezed in concentration kettle, after being concentrated into volume reducing 1/3 under 60-90 degree-0.08--0.09MPa vacuum condition, it is decrease temperature crystalline, the temperature of decrease temperature crystalline is 15-25 degree, finally by obtaining five water Sulfothiorine 2170kg, content 98.76% after filtration drying.
Embodiment 6
In 5000L reactor, add high density Sodium Sulphide waste water 3500kg(33%), industrial waste sulfur 499kg(95%), neutralized verdigris 1.7kg, starts to stir, and is warming up to 50 ℃, starts to pass into air, controls temperature of reaction 50
oc, reaction pressure is at 0.3MPa, after 12 hours, react complete, heat filtering after completion of the reaction, solid catalyst after filtration drops into recycled in reactor after collecting again, filtrate is squeezed in concentration kettle, after being concentrated into volume and reducing 1/3, is decrease temperature crystalline under 60-90 degree-0.08--0.09MPa vacuum condition, and the temperature of decrease temperature crystalline is 15-25 degree; Finally by obtaining five water Sulfothiorine 2105kg, content 98.60% after filtration drying.
Pass through the technical program, use cheap air as oxidation source, simultaneously by the use of composite catalyst, realized the Quick Oxidation under low-temp low-pressure, avoided existing industrialized unit under high temperature, condition of high voltage, to process the high operation cost problem that Sodium Sulphide waste water brings, gained by product sodium thiosulfate content is greater than 98.5% simultaneously, there is certain economic worth, and circulating mother liquor can recycle always, in whole treating processes, not having waste water to discharge, is the processing scheme of a set of complete environmental protection.
Below be only the part preferred embodiment of this programme; those skilled in the art can adopt other embodiment to realize completely within the protection domain of the technical program; the consumption of Sodium Sulphide waste liquid and sulfur waste sulphur and catalyzer, temperature of reaction, pressure and time; all can make the appropriate adjustments, at this, just not repeat one by one.
Claims (1)
1. a method of processing Sodium Sulphide waste water, it is characterized in that: to adding sodium sulphite mass concentration in 5000L reactor, be 36% high density Sodium Sulphide waste water 3600kg, the industrial waste sulfur 560kg of content 95%, the composite catalyst 1.8kg being mixed according to mass ratio 1:2 by aluminium sesquioxide and manganous sulfate, start to stir, be warming up to 70 ℃, start to pass into air, control temperature of reaction 70
oc, reaction pressure is at 0.1MPa, after 6 hours, react complete, heat filtering after completion of the reaction, solid catalyst after filtration drops into recycled in reactor after collecting again, filtrate is squeezed in concentration kettle, after being concentrated into volume and reducing 1/3, is decrease temperature crystalline under 60-90 degree-0.08 ~-0.09MPa vacuum condition, and the temperature of decrease temperature crystalline is 10-15 degree; After being dried after filtration, obtain five water Sulfothiorine.
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| CN105435795A (en) * | 2016-01-29 | 2016-03-30 | 于月光 | Method and application for preparing catalyst by using red mud as raw materials |
| CN109626655A (en) * | 2019-01-19 | 2019-04-16 | 江钨世泰科钨品有限公司 | A method of vulcanization cycling utilization of wastewater |
| CN113443753A (en) * | 2021-08-20 | 2021-09-28 | 宁波大地化工环保有限公司 | Treatment process of high-sulfur wastewater in metallurgical industry |
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| US5207927A (en) * | 1992-03-18 | 1993-05-04 | Uop | Treatment of an aqueous stream containing water-soluble inorganic sulfide compounds |
| CN1085190C (en) * | 1999-09-16 | 2002-05-22 | 海门市江滨化工二厂 | Cyctic utilization of waste water in the course of production of sodium thiosulfate |
| CN1166571C (en) * | 2002-02-01 | 2004-09-15 | 罗德春 | Integrated process for removing S, N and phenol from waste water containing S,N and phenol |
| CN101633495A (en) * | 2008-07-21 | 2010-01-27 | 蔡瑞琳 | Method for preparing sulphur black dye and sodium thiosulfate from sulphur dye waste water |
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Denomination of invention: A method for treating alkali sulfide wastewater Effective date of registration: 20211130 Granted publication date: 20140326 Pledgee: Dongying Hekou District sub branch of China Post Savings Bank Co.,Ltd. Pledgor: SHANDONG HUIHAI PHARMACEUTICAL& CHEMICAL Co.,Ltd. Registration number: Y2021980013568 |