CN208561864U - A kind of device being formed in situ and separate elemental sulfur - Google Patents
A kind of device being formed in situ and separate elemental sulfur Download PDFInfo
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- CN208561864U CN208561864U CN201821113451.6U CN201821113451U CN208561864U CN 208561864 U CN208561864 U CN 208561864U CN 201821113451 U CN201821113451 U CN 201821113451U CN 208561864 U CN208561864 U CN 208561864U
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Abstract
The utility model discloses a kind of device being formed in situ and separate elemental sulfur, including reaction unit, collection device, and seperation film is equipped in the reaction unit, and the seperation film is biomembrane-microfiltration membranes double-layer structure；The reaction unit is divided into reaction zone and accumulation regions by the seperation film, and the biomembrane is located at the reaction zone side, and the microfiltration membranes are located at the accumulation regions side；The collection device collects gas, liquid and the solid of the reaction unit discharge.The concept for being formed in situ and separating solid particulate matter is introduced membrane bioreactor by the utility model, the elemental sulfur that antimicrobial surface is formed is passed through into microfiltration membranes immediately using water flow pressure, and the elemental sulfur for passing through microfiltration membranes is collected in time, realize unidirectional biochemical reaction, i.e. sulfide oxidation becomes elemental sulfur, and elemental sulfur excessive oxidation or reduction will not occur.
Description
Technical field
The utility model relates to sewage treatment fields, and in particular to a kind of device being formed in situ and separate elemental sulfur.
Background technique
With China's rapid economic development, the raising of Public Environmental Awareness, governmental investment is increased, national waste water in 2015
COD total emission volumn reduced 11.37% compared with 2012, but still up to 2148.1 ten thousand tons.Wherein, quite a few derives from benzin
Refining papermaking, is butchered, pharmaceutical industry, be difficult to avoid that during these industry productions can generate containing sulfate, sulfide, ammonia nitrogen/
A large amount of waste water of nitrate, improper conduct oneself well of such waste water comprehends the great harmfulness of generation: (1) sulfate, excessive to arrange
It puts sulfate concentration in the water body that sulfate can make to improve, if just having bitterness containing higher sulfate (> 400mg/L) in water
Sense generates diarrhea if reaching 1000~1200mg/L and will lead to people；Secondly, often again rich in big in natural environment and waste water
The organic matter of amount, therefore sulfate is easily reduced to sulfide by sulfate reducing bacteria again, to generate secondary pollution.(2) sulphur
Compound has polar toxicity, corrosivity and breath malodor, and direct emission not only influences air quality, also can be to drainage pipeline
Corrosion is generated, directly biology in murder by poisoning water body.Environmental Protection in China portion not yet issues the report in relation to counting sulfide at present, according to the U.S.
Environment is affixed one's name in U.S.'s year pollutant statistical report of publication in 2015, and annual U.S.'s sulfide emission amount can reach U.S. row
It is of equal value in putting poison property Chemicals Directory to weight the 40% of toxic pollutant.(3) nitrate and ammonia nitrogen lead to nutriment in water body
Enrichment causes algae and the rapid breeding of other planktonic organisms, and then forms wawter bloom.Organic Wastewater Containing Sulfate can be by micro-
Sulfate reduction is sulfide by biology, and then sulfide oxidation is simple substance using nitrate as electron acceptor by microorganism
Sulphur；Sulfate reduction is then needed not move through containing waste water sulfide.People go microorganism using nitrate reduction vulcanisation
The technique of object is known as denitrification sulfur removal technology.For elemental sulfur as the intermediate product during sulfide oxidation, it is nontoxic and is solid
Body, can be used for agricultural fertilizer, industrial production after separating, recycling and improve soil acidification etc..
Pollutant exists in denitrification sulfur removal technology with three kinds of carbon, nitrogen, sulphur elements, and there are many valence state chemical combination in reaction process
Object participates in, and can reflect many kinds of substance form.Wherein carbon compound often with inorganic forms or organises substantially with the presence of+4 valences
Polymers morphology is present in reaction unit.Nitrogen compound then exists with inorganic forms, there is NO3 -、NO2 -、N2O、NO、N2, chemical valence
State is respectively+5 ,+4 ,+1 ,+2 and 0 valence.Sulphur compound valent state promising -2,0 ,+4 and+6 valence has inorganic sulfur in reaction unit
And organic sulfur, organic sulfur exist in the form of methyl mercaptan, dimethyl sulfide, dimethyl disulfide etc., it is main in inorganic sulfide compound
It will be with S2-、S0、S2O3 2-、SO4 2-Form exists.Therefore in denitrification desulfuration reaction device there are multiple functions microbe groups,
Microbial metabolism is complicated, and with microbial function, for example there are denitrifying bacterium, nitrogen-fixing bacteria, sulfur oxidizing bacterium, sulfate reducing bacteria, methane phases
Bacterium etc., there are a variety of mutual assistances and competition mechanisms, such as heterotroph to provide inorganic substrate for autotrophic bacterium inside activated sludge；Sulfate
Reducing bacteria provides substrate for sulfur oxidizing bacterium；Nitrate reduction bacterium and sulfate reducing bacteria competition organic substrates etc..
Activated sludge reaction device can not all solve sulphur peroxidating and mistake during sulfide oxidation in currently available technology
The problem of reduction, while needing multiple operating parameters (hydraulic detention time, influent load, ratio etc. between pollutant) accurate
And mutually adjust, elemental sulfur production rate is low.
In view of the above drawbacks, the utility model creator obtains originally practical new finally by prolonged research and practice
Type.
Utility model content
To solve above-mentioned technological deficiency, the technical solution adopted in the utility model is, provides one kind and is formed in situ and divides
Device from elemental sulfur, including reaction unit, collection device, the reaction unit is interior to be equipped with seperation film, and the seperation film is made a living
Object film-microfiltration membranes double-layer structure；
The reaction unit is divided into reaction zone and accumulation regions by the seperation film, and the biomembrane is located at the reaction zone one
Side, the microfiltration membranes are located at the accumulation regions side；
The collection device collects gas, liquid and the solid of the reaction unit discharge.
Preferably, the micro-filtration membrane aperture is greater than 20nm and less than 1 μm.
Preferably, the reaction unit connects a feed supplementing device, the feed supplementing device supplements waste water into the reaction zone.
Preferably, the reaction unit connects an argon gas steel cylinder by first pipe, the argon gas steel cylinder passes through the second pipe
Road connects the feed supplementing device, and the feed supplementing device connects the reaction unit by third pipeline.
Preferably, the nozzle of the third pipeline is located at the bottom end of the feed supplementing device.
Preferably, the collection device is divided into gas collector and fluid collection device, the gas collector is received
Collect gas, the fluid collection device collects liquid and solid.
Preferably, being equipped with valve between the reaction unit and the gas collector.
Preferably, the fluid collection device has solid-liquid separation function.
Preferably, the fluid collection device connects a water storage device, the fluid collection device and the water storage device
Between be equipped with peristaltic pump.
Preferably, being additionally provided with pressure gauge between the fluid collection device and the water storage device.
Compared with the prior art the utility model has the beneficial effects that:
1, the concept for being formed in situ and separating solid particulate matter is introduced membrane bioreactor by the utility model, utilizes water flow
The elemental sulfur that antimicrobial surface is formed is passed through microfiltration membranes by pressure immediately, and the elemental sulfur for passing through microfiltration membranes is collected in time, real
Unidirectional biochemical reaction is showed, i.e. sulfide oxidation becomes elemental sulfur, and elemental sulfur excessive oxidation or reduction will not occur.
2, the utility model, can also be by azotate pollution while removing sulphide removal and realizing that elemental sulfur recycles in situ
Object is reduced to nitrogen.
3, the sulfur-oxidizing bacteria biochemical reaction rate in the utility model reaction unit is much higher than in activated sludge reactor
The biochemical reaction rate of sulfur-oxidizing bacteria.
4, the utility model also achieves water filtration and purification on the basis of realizing waste water reclaiming.
Detailed description of the invention
It, below will be to institute in embodiment description in order to illustrate more clearly of the technical solution in various embodiments of the utility model
Attached drawing to be used is needed to be briefly described.
Fig. 1 is being formed in situ and separating elemental sulfur device configuration schematic diagram for the utility model embodiment one；
Fig. 2 is the rate of recovery and transmembrane pressure detection figure in the utility model embodiment two；
Fig. 3 is the concentration map of inorganic salts and organic salt in final solution in the utility model embodiment two；
Fig. 4 is the simple substance sulfur speciation and chemical analysis of elemental sulfur and activated sludge process recycling in the utility model embodiment two
Figure.
Digital representation in figure:
1- reaction unit, 11- long tube, 12- reaction are gone, the accumulation regions 13-, the first collection device of 2-, the 5th pipeline of 21-, 3-
Argon gas steel cylinder, 31- first pipe, 4- feed supplementing device, 41- second pipe, 42- third pipeline, the second collection device of 5-, 51-
Four pipelines, 6- water storage device, 7- pump, 8- pressure gauge, 9- valve.
Specific embodiment
Below in conjunction with attached drawing, the above and other technical features and advantages of the present invention are described in more detail.
Embodiment one
As shown in Figure 1, a kind of device being formed in situ and separate elemental sulfur of the utility model, including, reaction unit 1,
Fluid collection device 2, argon gas steel cylinder 3, feed supplementing device 4, gas collector 5, water storage device 6, pump 7, pressure gauge 8；Reaction dress
1 is set as biomembrane-microfiltration membranes complex reaction device, the lower section of reaction unit 1 is arranged in fluid collection device 2, and liquid collects dress
The elemental sulfur that reaction unit 1 generates can be collected by setting 2；Argon gas steel cylinder 3 is connected by first pipe 31 with reaction unit 1
It connects, argon gas steel cylinder 3 can be passed through argon gas into reaction unit 1, it is ensured that be always complete anaerobic environment in reaction unit 1, also guarantee
External and internal pressure is consistent in 1 system of reaction unit.
Feed supplementing device 4 is additionally provided between argon gas steel cylinder 3 and reaction unit 1, be inserted in feed supplementing device 4 second pipe 41 with
Third pipeline 42, second pipe 41 is for connecting feed supplementing device 4 and argon gas steel cylinder 3, and third pipeline 42 is for connecting feed supplementing device 4
With reaction unit 1；In feed supplementing device 4, the nozzle of second pipe 41 is located at the top of feed supplementing device 4, the pipe of third pipeline 42
Mouth is located at the bottom of feed supplementing device 4, and the waste water in feed supplementing device 4 is enabled to be passed to reaction dress when upper gas pressure is larger
It sets in 1.
The top of reaction unit 1 connects gas collector 5 by the 4th pipeline 51, is provided with valve on the 4th pipeline 51
9；A long tube 11 is arranged in the lower section of reaction unit 1, and long tube 11 is inserted into fluid collection device 2 up to fluid collection device 2
Bottom is also inserted with the 5th pipeline 21 inside fluid collection device 2, and the nozzle of the 5th pipeline 21 is higher than the nozzle height of long tube 11,
Fluid collection device 2 connects water storage device 6 by the 5th pipeline 21, is additionally provided with peristaltic pump 7 and pressure gauge 8 on the 5th pipeline 21.
As shown in Figure 1, being equipped with seperation film in reaction unit 1, seperation film divides reaction unit 1 for reaction zone 12 and accumulation regions
13, seperation film is biomembrane-microfiltration membranes double-layer structure, and wherein biomembrane is located at 12 side of reaction zone, and microfiltration membranes are located at accumulation regions
13 sides, accumulation regions 13 are located at the downside of reaction zone 12, and the liquid in reaction zone 12 has to pass through microfiltration membranes and can just enter
In accumulation regions 13, reaction unit 1 is connected to except pipeline with other devices, remaining place seals, it is ensured that the anaerobism in reaction unit 1
The stability of environment and pressure.
All devices seal in the present embodiment, guarantee the stability of the anaerobic environment and pressure in reaction unit 1.
The above-mentioned working principle being formed in situ and separate elemental sulfur device are as follows: when work, reaction unit 1 and liquid are collected and filled
Setting liquid in 2 is full state, and the liquid in fluid collection device 2 is constantly extracted into water storage device 6 after opening by peristaltic pump 7
In, the pressure in fluid collection device 2 is less than the pressure in reaction unit 1, so that liquid and elemental sulfur in reaction unit 1
Solid gravity and pressure drive it is lower be constantly flowed into fluid collection device 2, since reaction unit 1 seals, in feed supplementing device 4
Liquid also liquid flowed into reaction unit 1 under the twitch effect of peristaltic pump 7, argon gas steel cylinder 3 is constantly to reaction unit 1
In be filled with argon gas, it is ensured that the anaerobic state in reaction unit 1, argon gas steel cylinder 3 are also constantly filled with argon gas into feed supplementing device 4, really
Protect the balance of pressure in feed supplementing device 4；Contain sulfur oxidizing bacterium in biomembrane, sulfur oxidizing bacterium can turn respectively nitrate and organic matter
Nitrogen and carbon dioxide are turned to, sulfur oxidizing bacterium can convert elemental sulfur for sulfide；Micro-filtration membrane aperture is greater than 20nm and less than 1 μ
M, microfiltration membranes have selection filterability, and the diameter of elemental sulfur is less than 20nm, and the diameter of microorganism is greater than 1 μm, i.e. elemental sulfur
Grain may pass through microfiltration membranes, and microorganism is stopped by microfiltration membranes, realizes the separation of microorganism and elemental sulfur；Due to reaction unit 1
Separated by biomembrane and microfiltration membranes, there is nutrients/pollutant of the reaction zone 12 of biomembrane side containing more amount, without biology
The accumulation regions 13 of film side are then without or with a small amount of nutrients/pollutant, therefore forming material concentration difference, and then generate quilt
Dynamic transport, i.e. nutrients/pollutant can carry out transport across biological membranes along concentration gradient, due to sulfur-oxidizing bacteria sulphur oxidation and
Denitrifying enzyme system is present in biomembrane, under water flow pressure and concentration difference double influence, in reaction unit 1 on biomembrane
Sulfur-oxidizing bacteria biochemical reaction rate it is higher, sulfide can be reacted to form elemental sulfur on biomembrane, and micro-filtration
Film is placed at the immediate vicinity of biomembrane, and the elemental sulfur of formation can flow in liquid and pass through micro-filtration under gravity in time
Film, realization elemental sulfur is formed in situ and the separation process with biomembrane.The present embodiment only exists unidirectional life in reaction unit 1
Change reaction, i.e. for sulfide oxidation at elemental sulfur, reaction efficiency is high.
Embodiment two
According to the device of embodiment one being formed in situ and separate elemental sulfur, device is tested using different condition,
It tests as follows:
(1) test method
The device of embodiment one is tested using the solution of 8 kinds of different conditions, response parameter is as shown in table 1:
Parameters under the conditions of 1.8 kinds of table
The calculation formula of simple substance sulfur recovery rate R in test method are as follows:
R=(C1-C2)/C1
C1 is water inlet sulfide concentration in formula, and C2 is water outlet sulfide concentration.
As shown in table 1,8 conditions are subdivided into micro-filtration membrane aperture, water inlet component, initial inoculation amount.First group of micro-filtration fenestra
Diameter, which compares, includes: condition I, II, VI, the water inlet component of 3 kinds of conditions is constant, and (condition I is 0.22 μm, item to microfiltration membranes varying aperture
Part II is 0.45 μm, condition VI is 1.0 μm)；Second group of water inlet component compares comprising condition II, III, IV, V, micro-filtration membrane aperture
Constant, water inlet change of component changes three concentration of component of water inlet, acetic acid concentration in condition III based on condition II respectively
Concentration of nitric acid, which is increased in 500mg/L, condition IV, from the 115mg/L of condition II is increased to 500mg/ from the 120mg/L of condition II
L, the sulfide concentration of condition V is increased to 300mg/L from the 100mg/L of condition II；Third group initial inoculation amount, which compares, includes: item
Part VII, II, VIII, the water inlet component and micro-filtration membrane aperture of 3 kinds of conditions are constant, change the biomass of initial inoculum: condition
The biomass of initial inoculum is 5mL in VII, the biomass of initial inoculum is 10mL, originates in condition VIII in condition II
The biomass of inoculum is 20mL.
(2) test result
Fig. 2 is the operational effect of device under the conditions of 8 kinds, and predominantly detecting data includes that the elemental sulfur rate of recovery (is in Fig. 2
Elemental sulfur recovery rate or S0It recovery (is) Trans-Membrane in Fig. 2 with transmembrane pressure
Pressure or TMP), the condition that predominantly detects is 8 (they being Condition I~VIII in Fig. 2), and horizontal axis is device in Fig. 2
Runing time (Time)；As can be seen from Figure 2, in addition to condition V, remaining 7 condition simple substance sulfur recovery rate is all close to 100%, together
When reaction unit start 2 days after just close to 100%；And condition V is because the sulfide concentration of water inlet is increased to from 100mg/L
300mg/L；Meanwhile acetic acid in component of intaking and concentration of nitric acid are constant, it is insufficient to aoxidize 300mg/L sulphur to provide for microorganism
The electron acceptor of compound, so that cause the rate of recovery lower when calculating simple substance sulfur recovery rate R, but as can be seen from Figure 3, condition V's
The concentration of practical water outlet elemental sulfur is also close to 100mg/L.
Fig. 3 is the operational effect of device under the conditions of 8 kinds, and predominantly detecting water outlet acetate concentration (is Effluent in Fig. 2
Acetate), it is discharged nitrate concentration (being Effluent nitrate in Fig. 2), water outlet sulfide concentration (is in Fig. 2
Effluent sulfide), water outlet sulfate concentration (being Effluent sulfate in Fig. 2)；As can be seen from Figure 3, in addition to changing
Except condition III, IV, V of water inlet concentration of component, acetate and nitrate, sulfide, the sulfuric acid of the water outlet of remaining 5 condition
Salinity close to 0mg/L, the aqueous concentration of condition III, IV, V it is higher the reason is that, only change electron acceptor or the confession of water inlet
Body causes the electron donor of microbial consumption, the quantity of electron acceptor and rate uneven.
A, B, C are the elemental sulfur feature separated and recovered by the device in Fig. 4, and D, E, F are conventional activated sludge reaction
The elemental sulfur feature of device recycling；Elemental sulfur surface is smooth in Fig. 3 (A) and free from admixture；Elemental sulfur has crystal class in Fig. 3 (D)
Impurity, it can be seen that it contains the elements such as Mg, Na, K, C, O peak from EDX power spectrum.Fig. 3 (B), 3 (E) are XPS analysis, i.e. sulphur member
Plain valence state component analysis, 0 valence state accounts for the overwhelming majority in Fig. 3 (B), and the peak type in 3 (E) comprising+6 and-divalent.The analysis chart of XPS
3 (B), 3 (E) are consistent with the result of 3A, 3D, and Fig. 3 (C) and 3 (F) are XRD analysis, it was demonstrated that the substance of recycling is elemental sulfur.
The above is only the preferred embodiment of the present invention, is merely illustrative for the utility model, and
It is unrestricted.Those skilled in the art understand that can be to it in the spirit and scope defined by the utility model claims
Many changes, modifications, and even equivalents are carried out, but all will fall within the protection scope of the utility model.
Claims (10)
1. a kind of device being formed in situ and separate elemental sulfur, including reaction unit, collection device, which is characterized in that described anti-
It answers and is equipped with seperation film in device, the seperation film is biomembrane-microfiltration membranes double-layer structure；
The reaction unit is divided into reaction zone and accumulation regions by the seperation film, and the biomembrane is located at the reaction zone side,
The microfiltration membranes are located at the accumulation regions side；
The collection device collects gas, liquid and the solid of the reaction unit discharge.
2. being formed in situ and separating as described in claim 1 the device of elemental sulfur, which is characterized in that the micro-filtration membrane aperture is big
In 20nm and less than 1 μm.
3. being formed in situ and separating as described in claim 1 the device of elemental sulfur, which is characterized in that the reaction unit connection
One feed supplementing device, the feed supplementing device supplement waste water into the reaction zone.
4. being formed in situ and separating as claimed in claim 3 the device of elemental sulfur, which is characterized in that the reaction unit passes through
First pipe connects an argon gas steel cylinder, and the argon gas steel cylinder connects the feed supplementing device, the feed supplementing device by second pipe
The reaction unit is connected by third pipeline.
5. being formed in situ and separating as claimed in claim 4 the device of elemental sulfur, which is characterized in that the pipe of the third pipeline
Mouth is located at the bottom end of the feed supplementing device.
6. being formed in situ and separating as described in claim 1 the device of elemental sulfur, which is characterized in that the collection device is divided into
Gas collector and fluid collection device, the gas collector collect gas, and the fluid collection device collects liquid
With solid.
7. being formed in situ and separating as claimed in claim 6 the device of elemental sulfur, which is characterized in that the reaction unit and institute
It states and is equipped with valve between gas collector.
8. being formed in situ and separating as claimed in claim 6 the device of elemental sulfur, which is characterized in that the fluid collection device
With solid-liquid separation function.
9. being formed in situ and separating as claimed in claim 8 the device of elemental sulfur, which is characterized in that the fluid collection device
A water storage device is connected, peristaltic pump is equipped between the fluid collection device and the water storage device.
10. being formed in situ and separating as claimed in claim 9 the device of elemental sulfur, which is characterized in that the liquid collects dress
It sets and is additionally provided with pressure gauge between the water storage device.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201821113451.6U CN208561864U (en) | 2018-07-13 | 2018-07-13 | A kind of device being formed in situ and separate elemental sulfur |
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| CN201821113451.6U CN208561864U (en) | 2018-07-13 | 2018-07-13 | A kind of device being formed in situ and separate elemental sulfur |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108862867A (en) * | 2018-07-13 | 2018-11-23 | 哈尔滨工业大学 | A kind of device and method being formed in situ and separate elemental sulfur |
| CN110252207A (en) * | 2019-05-27 | 2019-09-20 | 陈祖友 | A kind of chemical reaction filter device convenient for extracting gas |
-
2018
- 2018-07-13 CN CN201821113451.6U patent/CN208561864U/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108862867A (en) * | 2018-07-13 | 2018-11-23 | 哈尔滨工业大学 | A kind of device and method being formed in situ and separate elemental sulfur |
| CN108862867B (en) * | 2018-07-13 | 2021-04-02 | 哈尔滨工业大学 | Device and method for in-situ formation and separation of elemental sulfur |
| CN110252207A (en) * | 2019-05-27 | 2019-09-20 | 陈祖友 | A kind of chemical reaction filter device convenient for extracting gas |
| CN110252207B (en) * | 2019-05-27 | 2021-07-27 | 山东沾化天元精细化工有限公司 | Chemical reaction filter equipment convenient to extract gas |
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