CN109293148A - A kind of processing unit and its processing method of sulfur-bearing brine waste - Google Patents
A kind of processing unit and its processing method of sulfur-bearing brine waste Download PDFInfo
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- CN109293148A CN109293148A CN201811255192.5A CN201811255192A CN109293148A CN 109293148 A CN109293148 A CN 109293148A CN 201811255192 A CN201811255192 A CN 201811255192A CN 109293148 A CN109293148 A CN 109293148A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The present invention provides the processing units and its processing method of a kind of sulfur-bearing brine waste, described device includes sequentially connected heat filtering unit, stripping unit, upgrading unit, physicochemical treatment unit and biochemical treatment unit, and the upgrading unit is also connected with burning unit.High-concentration sulfur-containing salt-containing organic wastewater is carried out heat filtering by the present invention, stripping, concentration, it burns, the operation such as materializing strategy and biochemical treatment, the collaboration processing operated by each unit, enable high-concentration sulfur-containing salt-containing organic wastewater efficient process, waste water after processing reaches national grade one discharge standard, the rate of recovery of element sulphur reaches 99% or more simultaneously, the salt of recycling also can reach National Industrial salt level-one and use standard, avoid the waste of resource, realize that it is recycled, reduce the processing cost of waste water, processing for other class organic wastewater with difficult degradation thereby provides reference.
Description
Technical field
The invention belongs to technical field of waste water processing, it is related to processing unit and its processing side of a kind of sulfur-bearing brine waste
Method.
Background technique
In recent years, with the continuous development of economy and human society, the bases such as dyestuff, medicine, pesticide and petrochemical industry
Industry also flourishes, and a large amount of waste water are inevitably discharged, and due to industrial nature, often contain in the waste water of discharge
There is sulfide, mainly the substances such as including hydrogen sulfide.Hydrogen sulfide is more toxic, and has the stronger ability of murdering to aquatile；?
Under the conditions of improper ventilation, when it gathers a certain concentration, can also toxic action be generated to operator.In addition, when containing sulphur
After the discharge of wastewater of compound is into water body, it can be reacted with the ferrous metal in water body, make the smelly nigrescence of water body, therefore, country is right
Sulfur-containing waste water has stringent discharge standard.
Currently, the common processing method of sulfur-containing waste water have it is following several: acidification absorption process, air- extraction, chemical flocculation, sky
Gas oxidizing process etc..Wherein, acidification absorption method is to make S in acid condition2-It is converted into H2S gas recycles it into desulfurizer
In sulphur there is certain risk, therefore to the more demanding of equipment since hydrogen sulfide has toxicity and corrosivity；Air lift
Method is to be come out the sulfide stripping in waste water using air, is limited in that energy consumption is larger, complex process, small to water,
The low waste water of sulfur content is simultaneously not suitable for；Chemical flocculation is to make itself and H by adding ferrous salt or molysite into waste water2S is generated
Removal is separated after insoluble solid, when sulfide concentration is excessively high, reagent consumption amount is more, is not suitable for the high, wastewater flow rate containing sulphur concentration
Big waste water；Air oxidation process, which refers to, is oxidized to sulphion nontoxic thiosulfate or sulfate using air, but due to
Solubility is lower in water for oxygen, and gas-liquid mass transfer efficiency is extremely low, it is unobvious to be passed through dioxygen oxidation effect merely, it is also necessary to phase be added
The catalyst answered improves treatment effect, and cost is caused to improve and increase the difficulty of subsequent processing.
Currently, the ingredient of sulfur-containing waste water is generally complex, single processing method is often difficult to reach ideal processing
Effect generallys use a variety for the treatment of measures and is jointly processed by waste water.106256783 A of CN discloses a kind of processing of sulfur-containing waste water
The pH of sulfur-containing waste water is adjusted to 4~6 using pH adjusting agent first by method, secondly bears the waste water input embrane method after adjusting pH
Desulfurization unit is pressed to carry out desulfurization process, the hydrogen sulfide gas of removing will cause atmosphere pollution through burning disposal, and embrane method is not applicable
In the processing of high slat-containing wastewater, film device easily blocks in the presence of high salt concentration.CN 106396185A discloses one
The processing method of kind sulphide-containing waste water, this method use oxidation-precipitation method, and it is laggard that acid solution adjusting pH is added into conditioning tank
Enter oxidation pond, is passed through filter if sulfide concentration is lower than 1mg/L after reaction with oxidant reaction and is filtered, if sulfide
Concentration is higher than 1mg/L, then introduces after precipitation reaction occurs for sedimentation basin and separate again, so that the sulphur in waste water is handled, but this method
It is suitable only for the waste water of low sulfur content, for high sulfur content waste water, not only aoxidizes at high cost, and a large amount of sludge can be generated,
Cost for wastewater treatment is considerably increased, and causes the waste of Sulphur ressource.
In addition to this, there are also other kinds of waste water in addition to sulfur content is higher, often salt content is also higher, treatment process
Also increasingly complex.108128983 A of CN discloses a kind of high sulfur-bearing, high saliferous gas field produced water deep purification process technique, packet
Include following steps: it is advanced that gas field recovered water sequentially enters natural subsidence unit-air bearing coagulant precipitation unit-evaporative crystallization unit-
Oxidation unit-biochemical treatment unit is handled, and pollutant is precipitated from sewage in the form of crystal salt, carry out landfill stabilization or
It recycles, but this method existing sulphur and other salts will only be precipitated jointly in the form of an ion, it is difficult to separation use is carried out,
And the sulphur of other forms is not recycled, the processing of waste water is not thorough.
In conclusion the processing of high-concentration sulfur-containing brine waste still needs to seek a kind of method efficiently, inexpensive, it both can be real
Existing discharged wastewater met the national standard, while effective component in waste water is recycled.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of processing units of sulfur-bearing brine waste
And its processing method, by the way that high-concentration sulfur-containing brine waste is successively carried out heat filtering, stripping, concentration, materializing strategy and life
The operations such as change processing sufficiently recycle element sulphur and salt in waste water, avoid the waste of resource, realize that it is recycled, simultaneously
So that waste water is reached national grade one discharge standard, reduces the processing cost of waste water.
To achieve this purpose, the present invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of processing unit of sulfur-bearing brine waste, described device includes sequentially connected
Heat filtering unit, stripping unit, upgrading unit, physicochemical treatment unit and biochemical treatment unit, the upgrading unit also with burning
Unit is connected.
In the present invention, since sulphur, salinity and content of organics are higher in the sulfur-bearing brine waste, a variety of lists are needed
Atom operation is jointly processed by, and recycles element sulphur by heat filtering unit and stripping unit, upgrading unit recycles salinity, materializing strategy list
Member and biochemical treatment cell processing low boiling point, volatile organic component, the high boiling organic matter of burning disposal cell processing are realized
The recycling of Sulphur ressource and salt also may be implemented in orderly, the efficient process of waste water, qualified discharge, realizes the recycling benefit of waste water
With being a set of environmentally protective processing unit.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the solid outlet of the heat filtering unit and the first dissolution filter unit phase
Even.
Preferably, it is additionally provided with the first pH between the heat filtering unit and stripping unit and adjusts unit.
In the present invention, it can be brought into sulphur simple substance to avoid hot melt solid using heat filtering, heat filtering unit removes sulphur removal list
After matter, remaining sulphur mainly exists in the form of sulphion, needs to blow out in the form of hydrogen sulfide in stripping unit, therefore, maintains
The temperature of heated effluent facilitates the stripping of subsequent hydrogen sulfide gas, avoids the waste of the energy, meanwhile, waste water is first adjusted before stripping
PH value makes it in acidity, and under acidic conditions, hydrogen sulfide is easier to stripping and comes out.
Preferably, it includes hydrochloric acid that the first pH, which adjusts regulator used in unit,.
Preferably, the gas vent of the stripping unit is connected with hydrogen sulfide absorption unit.
Preferably, it is air and/or nitrogen that the stripping unit is gases used.
Preferably, it is additionally provided with the 2nd pH between the stripping unit and upgrading unit and adjusts unit.
Preferably, it is alkali, preferably sodium hydroxide that the 2nd pH, which adjusts regulator used in unit,.
In the present invention, the pH of waste water is adjusted to neutrality substantially after stripping processing, it is possible to prevente effectively from acid waste water is to dense
The corrosiveness of evaporator in contracting unit, extends the service life of device.
As currently preferred technical solution, the upgrading unit includes MVR evaporator or multi-effect evaporator.
In the present invention, MVR evaporator refers to mechanical steam recompression evaporator, two generated using vapo(u)rization system itself
Low-grade steam is promoted to high-grade steam source through the mechanical work of compressor, can followed by secondary steam and its energy
Circumferential vapo(u)rization system provides thermal energy, to reduce the demand to outside resources；MVR evaporation belongs to energy saving skill with multiple-effect evaporation
Art can substantially reduce consumption neat in evaporation process, reduce processing cost.
Preferably, enter physicochemical treatment unit, the mother liquor of the upgrading unit after the volatile matter condensation of the upgrading unit
Into burning unit.
Preferably, the burning unit is connected with the second dissolution filter unit.
It is mainly the higher difficult volatile organic compounds of boiling point in the present invention, in mother liquor, ingredient is complex, and calorific value is higher, no
Suitable direct emission, burning disposal can effectively remove the part hardly degraded organic substance.
As currently preferred technical solution, the physicochemical treatment unit includes that air catalytic oxidation device, wet type are urged
Change any one in oxidation unit, Fenton oxidation device, iron-carbon micro-electrolysis device, device for catalyzing and oxidating ozone or Ultraviolet Oxidation device
Kind or at least two combination, combination typical case but non-limiting example has: air catalytic oxidation device and catalytic wet oxygen
Disguise the combination set, the combination of Fenton oxidation device and iron-carbon micro-electrolysis device, catalytic wet oxidation device, catalytic ozonation
Device and the combination of Ultraviolet Oxidation device etc..
In the present invention, by materializing strategy, the concentration of useless Organic substance in water can be effectively reduced, eliminate toxicity, while can
Biochemical is remarkably reinforced, and is convenient for subsequent biochemical treatment.
Preferably, the biochemical treatment unit includes anaerobic biochemical treatment device and/or contact oxidizing treatment device.
On the other hand, the present invention provides a kind of method using above-mentioned apparatus processing sulfur-bearing brine waste, the methods
Include: that sulfur-bearing brine waste is successively carried out to heat filtering processing, stripping processing, concentration, obtains volatile matter and mother liquor, it is described
Mother liquor carries out burning disposal, successively carries out materializing strategy and biochemical treatment after the volatile matter condensation, obtains waste water up to standard.
In the present invention, the sulfur-bearing brine waste is the waste water generated in silane coupler containing sulfur production process, is had
The distinguishing features such as machine object content height, high sulfur-bearing, acid strong, salinity height, biodegradability difference, need a variety of units operation common points
Reason, by heat filtering and stripping processing recycling element sulphur, concentration recycles salinity, and low boiling is decomposed in materializing strategy and biochemical treatment
Point, volatile organic component, the high boiling organic matter of burning disposal realize orderly, the efficient process of waste water, qualified discharge,
The resource utilization of waste water is realized in the recycling that Sulphur ressource and salt may be implemented, and is a kind of environmentally protective processing method.
As currently preferred technical solution, the sulfur-bearing brine waste is organic silicon waste water, and preferably silane is even
The waste water generated in connection agent production process.
Preferably, the COD value of the sulfur-bearing brine waste be 10000~40000mg/L, such as 10000mg/L,
15000mg/L, 20000mg/L, 25000mg/L, 30000mg/L, 35000mg/L or 40000mg/L etc., it is not limited to institute
The numerical value enumerated, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the temperature of the sulfur-bearing brine waste be 50~95 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C,
75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C or 95 DEG C etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable；PH value is 3~7, such as 3,3.5,4,4.5,5,5.5,6,6.5 or 7 etc., it is not limited to cited
Numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, in the sulfur-bearing brine waste sulfur content be 0.2~3wt%, such as 0.2wt%, 0.5wt%,
1wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt% etc., it is not limited to cited numerical value, in the numberical range its
His unlisted numerical value is equally applicable；Salt content be 25~35wt%, such as 25wt%, 26wt%, 28wt%, 30wt%,
32wt%, 34wt% or 35wt% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable.
Preferably, the temperature of the heat filtering processing is 50~95 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75
DEG C, 80 DEG C, 85 DEG C, 90 DEG C or 95 DEG C etc., it is not limited to cited numerical value, other unlisted numbers in the numberical range
It is worth equally applicable.
Preferably, the heat filtering processing obtained solid carries out dissolution filter, obtains elemental sulfur, gained sulphur simple substance is through overdrying
After dry processing can direct reuse in production.
Preferably, the temperature of steam condensate (SC) used in the dissolution filter be 60~90 DEG C, such as 60 DEG C, 65 DEG C, 70 DEG C,
75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable.
Preferably, the quality of steam condensate (SC) used is 5~15 times of handled amount of solid, such as 5 times, 6 times, 8 times, 10
Again, 12 times, 14 times or 15 times etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
Sample is applicable in.
Preferably, wastewater pH is adjusted after heat filtering processing to 1~7, such as 1,2,3,4,5,6 or 7 etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, pH adjusting agent used includes hydrochloric acid.
As currently preferred technical solution, the gases used stripping processing is air and/or nitrogen.
Preferably, the stripping handle when gas and waste water velocity ratio be 0.1~2, such as 0.1,0.3,0.5,0.8,
1,1.2,1.5,1.8 or 2 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
It is applicable in.
Preferably, the time of stripping processing is 0.5~5h, for example, 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h,
4h, 4.5h or 5h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the pressure of stripping processing is -0.02~-0.01MPa, for example, -0.02MPa, -0.018MPa, -
0.016MPa, -0.014MPa, -0.012MPa or -0.01MPa etc., it is not limited to cited numerical value, the numberical range
Other interior unlisted numerical value are equally applicable.
In the present invention, stripping processing carries out under the conditions of tiny structure, is more advantageous to the removing of hydrogen sulfide gas, will not be because
Vacuum degree is excessively high and causes the increase of processing cost.
Preferably, when the stripping is handled, waste water temperature is 20~90 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60
DEG C, 70 DEG C, 80 DEG C or 90 DEG C etc., it is not limited to cited numerical value, other unlisted numerical value are same in the numberical range
Sample is applicable in.
Preferably, the hydrogen sulfide gas that the stripping is handled is absorbed with lye.
Preferably, the lye is sodium hydroxide solution, and the feed liquid after absorbing hydrogen sulfide gas is processed can be made sulphur
Change sodium product.
Preferably, the concentration of the sodium hydroxide solution be 5~30wt%, such as 5wt%, 10wt%, 15wt%,
20wt%, 25wt% or 30wt% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable.
Preferably, wastewater pH is adjusted after stripping processing to 6~8, such as 6,6.5,7,7.5 or 8 etc., but is simultaneously not only limited
It is equally applicable in other unlisted numerical value in cited numerical value, the numberical range.
Preferably, pH adjusting agent used includes alkali, preferably sodium hydroxide.
As currently preferred technical solution, the concentration includes MVR evaporation process or multiple-effect evaporation processing.
Preferably, in the concentration, 1 ton of waste water consumption quantity of steam of every evaporation is 0.2~0.6 ton, such as 0.2 ton,
0.3 ton, 0.4 ton, 0.5 ton or 0.6 ton etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable.
Preferably, the solid salt that the concentration obtains includes sodium chloride, and obtained sodium chloride can achieve national work
Industry salt level-one uses standard.
Preferably, the COD value for the volatile matter condensate liquid that the concentration obtains is 5000~20000mg/L, such as
5000mg/L, 8000mg/L, 10000mg/L, 12000mg/L, 15000mg/L, 18000mg/L or 20000mg/L etc., but not
It is only limitted to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
In the present invention, the volatile matter that concentration obtains mainly includes low boiling point alcohols, silane coupling agent, siloxane oligomer
Object etc. is further processed after volatile matter condensation.
As currently preferred technical solution, the materializing strategy includes air catalytic oxidation, catalytic wet oxidation, sweet smell
Any one in oxidation, iron-carbon micro-electrolysis, catalytic ozonation or Ultraviolet Oxidation or at least two combination, the combination allusion quotation
Type but non-limiting example has: the combination of air catalytic oxidation and catalytic wet oxidation, iron-carbon micro-electrolysis and catalytic ozonation
Combination, Fenton oxidation, catalytic ozonation and combination of Ultraviolet Oxidation etc..
By materializing strategy, waste water is given to your organic concentration and is substantially reduced, and toxicity is eliminated, and biodegradability is obvious
Enhancing.
Preferably, after the materializing strategy, COD value of waste water be 500~5000mg/L, such as 500mg/L, 1000mg/L,
2000mg/L, 3000mg/L, 4000mg/L or 5000mg/L etc., it is not limited to cited numerical value, in the numberical range
Other unlisted numerical value are equally applicable；Sulfur content be 1.0~5.0mg/L, such as 1.0mg/L, 2.0mg/L, 3.0mg/L,
4.0mg/L or 5.0mg/L etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
It is applicable in.
Preferably, the biochemical treatment includes anaerobic biochemical treatment and/or catalytic oxidation processing.
Preferably, after the biochemical treatment, COD value of waste water be not more than 50mg/L, such as 50mg/L, 40mg/L, 30mg/L,
20mg/L or 10mg/L etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable
With；Sulfur content is no more than 1.0mg/L, such as 1.0mg/L, 0.8mg/L, 0.6mg/L, 0.4mg/L or 0.2mg/L etc., but not
It is only limitted to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
In the present invention, the country-level row of waste water is reached according to the COD value and sulfur content of the above waste water by biochemical treatment
Put standard (" integrated wastewater discharge standard " GB8978-1996).
As currently preferred technical solution, the temperature of the burning disposal is 300~600 DEG C, such as 300 DEG C, 350
DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C or 600 DEG C etc., it is not limited to cited numerical value, in the numberical range other
Unlisted numerical value is equally applicable.
Preferably, dissolution filter is carried out after the mother liquor burning disposal, gained filtrate is used for heat filtering processed waste water pH
Adjusting, obtained filter residue as solid waste processing.
In the present invention, most of in mother liquor is all higher boiling siloxane polymer, also includes unreacted raw material etc., ingredient
It is complex, if direct emission belongs to danger wastes, it will increase carrying capacity of environment, carrying out burning disposal can be such that organic matter sufficiently divides
Solution, since its calorific value is higher, heat when burning can also be made full use of.
Compared with prior art, the invention has the following advantages:
(1) present invention is handled by the collaboration that each unit operates, and high-concentration sulfur-containing salt-containing organic wastewater is enable efficiently to locate
Reason, waste water after processing reaches national grade one discharge standard, while the rate of recovery of element sulphur reaches 99% or more, the salt of recycling
Also it can reach National Industrial salt level-one and use standard；
(2) in waste water of the present invention element sulphur and salinity recycling, both avoided the waste of resource, can be realized its circulation benefit
With, can also reduce waste water post-processing difficulty and energy consumption；
(3) burning disposal of the present invention avoids the generation of a large amount of dangerous solid waste, greatly reduces at sewage
Manage cost；
(4) being effectively treated for sulfur-bearing saliferous organic silicon waste water can be other intractable organic silicon waste water in the present invention
Processing provides reference.
Detailed description of the invention
Fig. 1 is the annexation figure for the sulfur-bearing salt-containing waste water treating device that the embodiment of the present invention 1 provides；
Fig. 2 is the annexation figure for the sulfur-bearing salt-containing waste water treating device that the embodiment of the present invention 2 provides；
Fig. 3 is the annexation figure for the sulfur-bearing salt-containing waste water treating device that the embodiment of the present invention 3 provides；
Fig. 4 is the annexation figure for the sulfur-bearing salt-containing waste water treating device that the embodiment of the present invention 4 provides.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below to the present invention with specific embodiment party
Formula is further described.But following embodiments is only simple example of the invention, does not represent or limits and is of the invention
Rights protection scope, the scope of the present invention are subject to claims.
Specific embodiment of the invention part provides the processing unit and its processing method of a kind of sulfur-bearing brine waste, institute
Stating device includes sequentially connected heat filtering unit, stripping unit, upgrading unit, physicochemical treatment unit and biochemical treatment unit,
The upgrading unit is also connected with burning unit.
It the treating method comprises: sulfur-bearing brine waste is successively carried out to heat filtering processing, stripping processing, concentration,
Volatile matter and mother liquor are obtained, the mother liquor carries out burning disposal, successively carries out materializing strategy and biochemistry after the volatile matter condensation
Processing, obtains waste water up to standard.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1:
The processing unit and its processing method of a kind of sulfur-bearing brine waste are present embodiments provided, the connection of described device is closed
System's figure is as shown in Figure 1, include at sequentially connected heat filtering unit, stripping unit, upgrading unit, physicochemical treatment unit and biochemistry
Unit is managed, the upgrading unit is also connected with burning unit.
The solid outlet of the heat filtering unit is connected with the first dissolution filter unit, the heat filtering unit and stripping list
It is additionally provided with the first pH between member and adjusts unit, the gas vent of the stripping unit is connected with hydrogen sulfide absorption unit, described to blow
The 2nd pH, which is additionally provided with, between de- unit and upgrading unit adjusts unit.
The upgrading unit includes MVR evaporator, and the physicochemical treatment unit includes iron-carbon micro-electrolysis device, the biochemistry
Processing unit includes contact oxidizing treatment device, and the burning unit is connected with the second dissolution filter unit.
Include: using the method that above-mentioned apparatus handles sulfur-bearing brine waste
It (1) is 80 DEG C by temperature, COD value 20000mg/L, sulfur content 2wt%, sodium chloride content 35wt%, pH
Heat filtering processing is carried out for 6 silane coupled agent production waste water 1000kg, obtaining filter residue is 5kg, and 30kg is added into filter residue and steams
Vapour condensed water carries out dissolution filter, and obtained insoluble matter is sulphur simple substance, and filtrate enters MVR evaporator；
It (2) is 4 by the Nacl acid for adjusting pH value that the waste water after heat filtering is 30wt% with concentration；
(3) waste water after step (2) to be adjusted to pH carries out stripping processing, guarantee during stripping system pressure be-
0.01MPa, air velocity are 1L min-1, stripping time 3h, water temperature is 70~80 DEG C, and the hydrogen sulfide gas that stripping obtains is used
Absorbing by liquid caustic soda is 15mg/L through stripping treated waste water sulfur content；
(4) stripping treated waste water lye is adjusted pH value is 7.5；
(5) waste water after step (4) to be adjusted to pH carries out the processing of MVR evaporation and concentration, and the water and organic volatile matter of evaporation are cold
Condensate liquid is obtained after solidifying；The salt being concentrated to get can be used as Nacl use；Remaining mother liquor burning disposal at a temperature of 500 DEG C, then
Through dissolution filter, gained filtrate is adjusted for wastewater pH in step (2)；
(6) condensate liquid that the COD for obtaining step (5) is 15000mg/L carries out iron-carbon micro-electrolysis processing, processed waste water
COD is 5000mg/L, sulfur content 2.0mg/L；
(7) step (6) treated waste water is subjected to catalytic oxidation processing, the COD of processed waste water is 48mg/L, and sulphur contains
Amount is 0.8mg/L, reaches national grade one discharge standard.
Embodiment 2:
The processing unit and its processing method of a kind of sulfur-bearing brine waste are present embodiments provided, the connection of described device is closed
System's figure is as shown in Fig. 2, include at sequentially connected heat filtering unit, stripping unit, upgrading unit, physicochemical treatment unit and biochemistry
Unit is managed, the upgrading unit is also connected with burning unit.
The solid outlet of the heat filtering unit is connected with the first dissolution filter unit, the heat filtering unit and stripping list
It is additionally provided with the first pH between member and adjusts unit, the gas vent of the stripping unit is connected with hydrogen sulfide absorption unit, described to blow
The 2nd pH, which is additionally provided with, between de- unit and upgrading unit adjusts unit.
The upgrading unit includes MVR evaporator, and the physicochemical treatment unit includes catalytic wet oxidation device, the life
Changing processing unit includes contact oxidizing treatment device, and the burning unit is connected with the second dissolution filter unit.
Include: using the method that above-mentioned apparatus handles sulfur-bearing brine waste
It (1) is 60 DEG C by temperature, COD value 40000mg/L, sulfur content 3wt%, sodium chloride content 30wt%, pH
Heat filtering processing is carried out for 7 silane coupled agent production waste water 1000kg, obtaining filter residue is 2kg, and 30kg is added into filter residue and steams
Vapour condensed water carries out dissolution filter, and obtained insoluble matter is sulphur simple substance, and filtrate enters MVR evaporator；
It (2) is 3 by the Nacl acid for adjusting pH value that the waste water after heat filtering is 30wt% with concentration；
(3) waste water after step (2) to be adjusted to pH carries out stripping processing, guarantee during stripping system pressure be-
0.02MPa, air velocity are 0.5L min-1, stripping time 2h, water temperature is 40~50 DEG C, the hydrogen sulfide gas that stripping obtains
With absorbing by liquid caustic soda, through stripping, treated that waste water sulfur content is 15mg/L；
(4) stripping treated waste water lye is adjusted pH value is 7；
(5) waste water after step (4) to be adjusted to pH carries out the processing of MVR evaporation and concentration, and the water and organic volatile matter of evaporation are cold
Condensate liquid is obtained after solidifying；The salt being concentrated to get can be used as Nacl use；Remaining mother liquor burning disposal at a temperature of 600 DEG C, then
Through dissolution filter, gained filtrate is adjusted for wastewater pH in step (2)；
(6) condensate liquid that the COD for obtaining step (5) is 20000mg/L carries out catalytic wet oxidation processing, gives up after processing
Water COD is 500mg/L, sulfur content 3.5mg/L；
(7) step (6) treated waste water is subjected to catalytic oxidation processing, the COD of processed waste water is 20mg/L, and sulphur contains
Amount is 0.5mg/L, reaches national grade one discharge standard.
Embodiment 3:
The processing unit and its processing method of a kind of sulfur-bearing brine waste are present embodiments provided, the connection of described device is closed
System's figure is as shown in figure 3, include at sequentially connected heat filtering unit, stripping unit, upgrading unit, physicochemical treatment unit and biochemistry
Unit is managed, the upgrading unit is also connected with burning unit.
The solid outlet of the heat filtering unit is connected with the first dissolution filter unit, the gas vent of the stripping unit
It is connected with hydrogen sulfide absorption unit, pH is additionally provided between the stripping unit and upgrading unit and adjusts unit.
The upgrading unit includes four-effect evaporator, and the physicochemical treatment unit includes Fenton oxidation device, the biochemistry
Processing unit includes anaerobic biochemical treatment device and contact oxidizing treatment device, the burning unit and the second dissolution filter unit
It is connected.
Include: using the method that above-mentioned apparatus handles sulfur-bearing brine waste
It (1) is 50 DEG C by temperature, COD value 10000mg/L, sulfur content 1wt%, sodium chloride content 25wt%, pH
Heat filtering processing is carried out for 3 silane coupled agent production waste water 1000kg, obtaining filter residue is 3kg, and 27kg is added into filter residue and steams
Vapour condensed water carries out dissolution filter, and obtained insoluble matter is sulphur simple substance, and filtrate enters four-effect evaporator；
(2) waste water after heat filtering is subjected to stripping processing, guarantees that system pressure is -0.016MPa during stripping, it is empty
Gas velocity is 2L min-1, stripping time 1h, water temperature is 20~30 DEG C, the hydrogen sulfide gas absorbing by liquid caustic soda that stripping obtains, warp
Stripping treated waste water sulfur content is 50mg/L；
(3) stripping treated waste water lye is adjusted pH value is 6；
(4) waste water after step (3) to be adjusted to pH carries out four-effect evaporation concentration, and the water and organic volatile matter of evaporation are cold
Condensate liquid is obtained after solidifying；The salt being concentrated to get can be used as Nacl use；Remaining mother liquor burning disposal at a temperature of 400 DEG C, then
Through dissolution filter, gained filtrate is adjusted for wastewater pH in step (3)；
(5) condensate liquid that the COD for obtaining step (4) is 5000mg/L carries out Fenton oxidation processing, processed waste water COD
For 3500mg/L, sulfur content 3.0mg/L；
(6) step (5) treated waste water successively carries out anaerobic biochemical treatment and catalytic oxidation are handled, processed waste water
COD be 42mg/L, sulfur content 1.0mg/L reaches national grade one discharge standard.
Embodiment 4:
The processing unit and its processing method of a kind of sulfur-bearing brine waste are present embodiments provided, the connection of described device is closed
System's figure is as shown in figure 4, include at sequentially connected heat filtering unit, stripping unit, upgrading unit, physicochemical treatment unit and biochemistry
Unit is managed, the upgrading unit is also connected with burning unit.
The solid outlet of the heat filtering unit is connected with the first dissolution filter unit, the heat filtering unit and stripping list
It is additionally provided with the first pH between member and adjusts unit, the gas vent of the stripping unit is connected with hydrogen sulfide absorption unit, described to blow
The 2nd pH, which is additionally provided with, between de- unit and upgrading unit adjusts unit.
The upgrading unit includes double effect evaporator, and the physicochemical treatment unit includes air catalytic oxidation device and ozone
Catalytic oxidizing equipment, the biochemical treatment unit includes contact oxidizing treatment device, the burning unit and the second dissolution filter
Unit is connected.
Include: using the method that above-mentioned apparatus handles sulfur-bearing brine waste
(1) be 95 DEG C by temperature, COD value 30000mg/L, sulfur content 0.5wt%, sodium chloride content 33wt%,
The silane coupled agent production waste water 1000kg that pH is 5 carries out heat filtering processing, and obtaining filter residue is 3kg, and 36kg is added into filter residue
Steam condensate (SC) carries out dissolution filter, and obtained insoluble matter is sulphur simple substance, and filtrate enters double effect evaporator；
It (2) is 1 by the Nacl acid for adjusting pH value that the waste water after heat filtering is 30wt% with concentration；
(3) waste water after step (2) to be adjusted to pH carries out stripping processing, guarantee during stripping system pressure be-
0.012MPa, air velocity are 0.2L min-1, stripping time 5h, water temperature is 80~90 DEG C, the hydrogen sulfide gas that stripping obtains
With absorbing by liquid caustic soda, through stripping, treated that waste water sulfur content is 20mg/L；
(4) stripping treated waste water lye is adjusted pH value is 8；
(5) waste water after step (4) to be adjusted to pH carries out double-effect evaporation concentration, and the water and organic volatile matter of evaporation are cold
Condensate liquid is obtained after solidifying；The salt being concentrated to get can be used as Nacl use；Remaining mother liquor burning disposal at a temperature of 300 DEG C, then
Through dissolution filter, gained filtrate is adjusted for wastewater pH in step (2)；
(6) condensate liquid that the COD for obtaining step (5) is 9000mg/L carries out air catalytic oxidation processing, gives up after processing
Water COD is 4000mg/L, sulfur content 3.0mg/L；
(7) step (6) treated waste water being subjected to catalytic ozonation processing, processed waste water COD is 800mg/L,
Sulfur content is 2.0mg/L；
(8) step (7) treated waste water is subjected to catalytic oxidation processing, the COD of processed waste water is 47mg/L, and sulphur contains
Amount is 0.9mg/L, reaches national grade one discharge standard.
Based on the above embodiments as can be seen that each primary unit operation heat filtering in the present invention, stripping, concentration, at materialization
Reason, biochemical treatment, burning etc., which are jointly processed by sulfur-bearing brine waste, can just enable its efficient process, and waste water after processing reaches
National grade one discharge standard, while the rate of recovery of element sulphur reaches 99% or more, the salt of recycling also can reach National Industrial salt one
Grade uses standard；And lack any one, it can all make waste water be unable to reach discharge standard or generate a large amount of dangerous solids and give up
Gurry increases the processing cost of waste water.
The Applicant declares that the present invention is explained by the above embodiments detailed device and process of the invention, but this
Invention is not limited to above-mentioned apparatus and method, that is, does not mean that the present invention must rely on above-mentioned apparatus and method and could implement.
It should be clear to those skilled in the art, any improvement in the present invention, to the equivalence replacement of invention unit operation
And addition, selection of concrete mode of auxiliary operation etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of processing unit of sulfur-bearing brine waste, which is characterized in that described device include sequentially connected heat filtering unit,
Stripping unit, upgrading unit, physicochemical treatment unit and biochemical treatment unit, the upgrading unit are also connected with burning unit.
2. processing unit according to claim 1, which is characterized in that the solid outlet of the heat filtering unit and first molten
Filter element is solved to be connected；
Preferably, it is additionally provided with the first pH between the heat filtering unit and stripping unit and adjusts unit；
Preferably, it includes hydrochloric acid that the first pH, which adjusts regulator used in unit,；
Preferably, the gas vent of the stripping unit is connected with hydrogen sulfide absorption unit；
Preferably, it is air and/or nitrogen that the stripping unit is gases used；
Preferably, it is additionally provided with the 2nd pH between the stripping unit and upgrading unit and adjusts unit；
Preferably, it is alkali, preferably sodium hydroxide that the 2nd pH, which adjusts regulator used in unit,.
3. processing unit according to claim 1 or 2, which is characterized in that the upgrading unit includes MVR evaporator or more
Imitate evaporator；
Preferably, enter physicochemical treatment unit after the volatile matter condensation of the upgrading unit, the mother liquor of the upgrading unit enters
Burn unit；
Preferably, the burning unit is connected with the second dissolution filter unit.
4. processing unit according to claim 1-3, which is characterized in that the physicochemical treatment unit includes air
Catalytic oxidizing equipment, catalytic wet oxidation device, Fenton oxidation device, iron-carbon micro-electrolysis device, device for catalyzing and oxidating ozone or
Any one in Ultraviolet Oxidation device or at least two combination；
Preferably, the biochemical treatment unit includes anaerobic biochemical treatment device and/or contact oxidizing treatment device.
5. a kind of method using any one of claim 1-4 described device processing sulfur-bearing brine waste, which is characterized in that described
Method includes: that sulfur-bearing brine waste is successively carried out to heat filtering processing, stripping processing, concentration, obtains volatile matter and mother liquor,
The mother liquor carries out burning disposal, successively carries out materializing strategy and biochemical treatment after the volatile matter condensation, obtains waste water up to standard.
6. according to the method described in claim 5, it is characterized in that, the sulfur-bearing brine waste is organic silicon waste water, preferably
For the waste water generated in silane coupling agent production process；
Preferably, the COD value of the sulfur-bearing brine waste is 10000~40000mg/L；
Preferably, the temperature of the sulfur-bearing brine waste is 50~95 DEG C, and pH value is 3~7；
Preferably, sulfur content is 0.2~3wt% in the sulfur-bearing brine waste, and salt content is 25~35wt%；
Preferably, the temperature of the heat filtering processing is 50~95 DEG C；
Preferably, the heat filtering processing obtained solid carries out dissolution filter, obtains elemental sulfur；
Preferably, the temperature of steam condensate (SC) used in the dissolution filter is 60~90 DEG C；
Preferably, the quality of steam condensate (SC) used is 5~15 times of handled amount of solid；
Preferably, wastewater pH is adjusted to 1~7 after the heat filtering processing；
Preferably, pH adjusting agent used includes hydrochloric acid.
7. method according to claim 5 or 6, which is characterized in that the gases used stripping processing is air and/or nitrogen
Gas；
Preferably, the velocity ratio of gas and waste water is 0.1~2 when the stripping is handled；
Preferably, the time of the stripping processing is 0.5~5h；
Preferably, the pressure of the stripping processing is -0.02~-0.01MPa；
Preferably, when the stripping is handled, waste water temperature is 20~90 DEG C；
Preferably, the hydrogen sulfide gas that the stripping is handled is absorbed with lye；
Preferably, the lye is sodium hydroxide solution；
Preferably, the concentration of the sodium hydroxide solution is 5~30wt%；
Preferably, wastewater pH is adjusted to 6~8 after the stripping processing；
Preferably, pH adjusting agent used includes alkali, preferably sodium hydroxide.
8. according to the described in any item methods of claim 5-7, which is characterized in that the concentration includes MVR evaporation process
Or multiple-effect evaporation processing；
Preferably, in the concentration, every 1 ton of waste water consumption quantity of steam of evaporation is 0.2~0.6 ton；
Preferably, the solid salt that the concentration obtains includes sodium chloride；
Preferably, the COD value for the volatile matter condensate liquid that the concentration obtains is 5000~20000mg/L.
9. according to the described in any item methods of claim 5-8, which is characterized in that the materializing strategy includes air catalytic oxygen
Any one in change, catalytic wet oxidation, Fenton oxidation, iron-carbon micro-electrolysis, catalytic ozonation or Ultraviolet Oxidation or at least two
The combination of kind；
Preferably, after the materializing strategy, COD value of waste water is 500~5000mg/L, and sulfur content is 1.0~5.0mg/L；
Preferably, the biochemical treatment includes anaerobic biochemical treatment and/or catalytic oxidation processing；
Preferably, after the biochemical treatment, COD value of waste water is not more than 50mg/L, and sulfur content is not more than 1.0mg/L.
10. according to the described in any item methods of claim 5-9, which is characterized in that the temperature of the burning disposal be 300~
600℃；
Preferably, dissolution filter is carried out after the mother liquor burning disposal, gained filtrate is used for the tune of heat filtering processed waste water pH
Section.
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