CN110395835A - Microbial fermentation produces high ammonia-nitrogen wastewater and automobile produces NOxThe device and method of coupling processing - Google Patents
Microbial fermentation produces high ammonia-nitrogen wastewater and automobile produces NOxThe device and method of coupling processing Download PDFInfo
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Abstract
High ammonia-nitrogen wastewater is produced the present invention relates to microbial fermentation and automobile produces NOxThe apparatus and method of coupling processing, wherein microbial fermentation produce high ammonia-nitrogen wastewater come from kasugarnycin acidifying fermentation liquid, high ammonia-nitrogen wastewater of the fermentation liquid through nanofiltration and ion exchange, the waste water holding vessel after mixing, high-pressure pump is pumped into high ammonia-nitrogen wastewater destilling tower, wherein distilling NH3Enter through input channel and anhydrous SrCl is housed2Reactor, in its reactor, anhydrous SrCl2It is reacted with ammonia and generates Sr(NH3)(8‑x)Cl2, the Sr(NH of generation3)(8‑x)Cl2It is decomposed at a temperature of 100~300 DEG C and generates NH3, generate NH3With automobile NOxReaction generates N2After be discharged.The present invention is different from usual automobile NOxProcessing is seen as two independent events with microbial fermentation production high ammonia-nitrogen wastewater processing and is studied, and the present invention is combined, and can well be made full use of the ammonia nitrogen that microbial fermentation produces high ammonia-nitrogen wastewater, moreover it is possible to reduce vehicle exhaust NOxDischarge.In addition, decomposing NH under the present invention and urea high temperature3, the NH that then decomposes3Restore NOxCompared to comparing, it is more suitable for low temperature environment and urea pyrolytic is overcome to produce this disadvantage of cyanuric acid plug nozzle.
Description
Technical field
The invention belongs to fermentation technical fields, are related to microbial fermentation and produce high ammonia-nitrogen wastewater and automobile production NOxCoupling processing
Device and method more specifically be related to streptomyces microaureus fermentation and produce high ammonia-nitrogen wastewater and automobile producing NOxCoupling processing
Device and method.
Background technique
Microbial fermentation, which is related to field, the numerous areas such as food, feed, medicine and biological pesticide industry, microorganism hair
Ferment ingredient requirement must satisfy the demand of the elements such as C, N, P, S, and the carbohydrates such as nature protein, lipid, carbohydrate are basic
Meet microorganism growth demand.No matter take single microorganism fermentation or mixed function microbial fermentation, final purpose are logical
Microbial fermentation is crossed to obtain the product of human needs and simultaneously carry out at harmless method organic wastewater with difficult degradation thereby and solid waste
Reason.Single microorganism fermentation is expected to obtain the antibiotic for having preventive and therapeutic effect to animals and plants and disease microorganism, and animal and plant growth needs
The enzyme protein preparation etc. that the amino acid and industry wanted need；Mixed microorganism fermentation be expected to obtain biological organic fertilizer, biomass energy,
Fermented feed and food etc..No matter single microorganism fermentation or mixed microorganism, produced fermentation liquid contain human needs'
Substance such as antibiotic, amino acid, vitamin, microelement, polypeptide and pigment etc..Object is used to these substance separation purifying techniques
The method of reason, chemistry and biology, generallys use ion exchange resin, chromatographic column, reverse osmosis membrane, ceramics during isolating and purifying
After the group technologies such as film, nanofiltration membrane, Solid Phase Extraction, product required for us could be obtained.These fermentation liquids especially antibiosis
High ammonia-nitrogen wastewater is often generated during the isolation and purification of element, these high ammonia-nitrogen wastewaters are not preprocessed to be just directly entered sewage
Factory, these not preprocessed high ammonia-nitrogen wastewaters into sewage plant not only increase the load of NH_3-N treating, and destroy at sewage
The activated sludge performance of factory is managed, further increases sludge sewage culture expense, to increase at enterprise's sewage
The expense of reason.
From on July 1st, 2013, Chinese Ministry of Environmental Protection's publication bulletin required the bavin of all productions, import, sale and registration
Oil turbine and automobile have to comply with state's IV standard (including nitrogen oxides and PM2.5).With the Fang Xing of domestic automobile industry
It does not end, more than 200,000,000, so more vehicles certainly will cause draw the various vehicles of China Today to the atmospheric environment of human survival
The destruction stayed, further influences human health.The nitrogen oxides and PM2.5 for how handling vehicle exhaust become current research
Hot spot；Three-protection design in current national requirements fermentation industry must reach the national three waste discharge standard in relation to fermentation industry,
Therefore high ammonia-nitrogen wastewater processing also becomes the research hotspot of fermentation industry.And it is current in relation to automobile industry to nitrogen oxides and
The processing of PM2.5 and the high ammonia-nitrogen wastewater processing of fermentation industry are isolated by researcher, do not form the connection of a certainty
It is studied.
Vehicle discharged nitrous oxides processing system technology utilizes NH3Reducing agent is made, under the action of catalyst, by NOxReduction
For N2, it is control fixation or mobile pollution source NOxA kind of effective measures of discharge.Automobile industry generally receives urea vehicle
Discharged nitrous oxides processing system is that large diesel engine reaches V or will execute the solution of VI standard, EGR(control burning
Ammonia oxygen drops)+DOC(diesel oil oxidation catalyst converter)+PDF(diesel oil organic granular captures regenerator) system is middle light diesel engine
Reach V or the solution of VI standard will be executed.The V discharge standard of the confidential satisfaction country of heavy-duty diesel oil, most researchers
The consistent technology path that nitrogen oxides and PM2.5 are solved using the following two kinds: first is that reducing of diesel engine by improving burning
Grain object (PM2.5) raw emissions, then utilize aqueous solution of urea, ammonia are hydrolyzed into, as reducing agent, into one in exhaust system
It walks NOxIt is reduced into N2；Second is that reducing NO in machine by EGR using DPF+EGR routex, utilized in exhaust system
DPF(also has using POC's) reduction is granular material discharged (PM2.5), to meet the requirement of emission regulation.Utilize urea resolving system
System produces NH3By the NO of automobilexRestore N2Temperature requirement is at least above 200 DEG C and is lower than 380 DEG C before must satisfy catalyst
It is required that temperature is lower than 200 DEG C, urea decomposes that ammonia amount is low or catalyst low efficiency, cannot be complete by the urea in nozzle
Ammonia is resolved into entirely, and when temperature is higher than 380 DEG C, the possible fast dewatering of the aqueous solution of urea sprayed into exhaust airstream is transformed into trimerization
Cyanic acid is to plug nozzle.How disadvantages mentioned above is solved, and researchers are handled by efficiency compact high vehicle discharged nitrous oxides
Principle, design and the Related product development of system meet NH3By the NO of automobilexRestore N2Demand.Although current using efficiently tight
Type vehicle discharged nitrous oxides processing system of gathering handles nitrogen oxides, should include that urea decomposes storage tank, control system, ammonia metering
Spraying system etc., but principle still utilizes the decomposition ammonia of urea by NOxRestore N2, how directly directly to be restored using ammonia
Gas decomposes NOx, the NO of the ammonia reduction vehicle exhaust of high ammonia-nitrogen wastewater is produced especially with microbial fermentationx, so far both at home and abroad
There are no relevant patents and paper to report.
Summary of the invention
In order to solve the problems in the existing technology, the present invention provides a kind of microbial fermentation and produces high ammonia-nitrogen wastewater and vapour
Vehicle NOxThe apparatus and method of coupling processing, wherein microbial fermentation produces high ammonia-nitrogen wastewater and comes from kasugarnycin acidifying fermentation liquid, should
High ammonia-nitrogen wastewater of the fermentation liquid through nanofiltration and ion exchange, waste water holding vessel after mixing, high-pressure pump is pumped into high ammonia nitrogen
Waste water destilling tower, the NH that ammonia nitrogen waste water volatilizees through destilling tower (6)3It is delivered to equipped with anhydrous SrCl2NH3Adsorptive reactor (7),
In NH3Adsorptive reactor (7) generates Sr(NH3)(8-x)Cl2, Sr(NH3)(8-x)Cl2Through material conveying pipe to (8), Sr
(NH3)(8-x)Cl2It is decomposed in (8) high temperature and produces NH3, produced NH3While the NO with collection automobilexIt carries out reaction and generates N2And H2O,
Final N2It is discharged into atmosphere.The present invention is different from usual automobile NOxProcessing produces high ammonia-nitrogen wastewater processing with microbial fermentation and is seen
It is studied at two independent events, the present invention is combined, and microbial fermentation can be produced high ammonia-nitrogen wastewater well
Ammonia nitrogen makes full use of, moreover it is possible to reduce vehicle exhaust NOxDischarge.NH is produced in addition, decomposing under the present invention and urea high temperature3, then divide
The NH of solution3Restore NOxIt compares, be more suitable for low temperature environment and urea pyrolytic is overcome to produce this disadvantage of cyanuric acid plug nozzle.
In order to realize that goal of the invention, the present invention adopt the following technical scheme that:
A kind of microbial fermentation produces high ammonia-nitrogen wastewater and automobile NOxThe device of coupling processing, the device include nanofiltration membrane
(3), ion exchange resin (4), high ammonia-nitrogen wastewater holding vessel (5), high ammonia-nitrogen wastewater destilling tower (6), ammonia and SrCl2Reaction
Reactor (7) and NOxReduction reactor (8), wherein polysulfones nanofiltration membrane liquid and ceramic membrane filtration liquid are respectively via nanofiltration membrane
(3) and after ion exchange resin (4) processing, into high ammonia-nitrogen wastewater holding vessel (5), then high ammonia-nitrogen wastewater destilling tower is passed sequentially through
(6), ammonia and SrCl2The reactor (7) and NO of reactionxReduction reactor (8).
In the preferred embodiments of the present invention, the polysulfones nanofiltration membrane liquid is that the spring thunder through ion exchange is mould
Plain concentrate；The ceramic membrane filtration liquid is the kasugarnycin fermentation liquid through ceramic membrane filter, is acidified fermentation
Liquid.
In the preferred embodiments of the present invention, the ion exchange resin is preferably cation (H+Type) ion friendship
Change resin.
In the preferred embodiments of the present invention, high ammonia-nitrogen wastewater destilling tower (6) is MVR reactor.
The present invention also protects a kind of microbial fermentation to produce high ammonia-nitrogen wastewater and automobile NOxThe method of coupling processing, including with
Lower step:
(1) the kasugarnycin fermentation liquid through ceramic membrane filter is mould with polysulfones nanofiltration membrane spring thunder by ion exchange resin treatment
Element exchange liquid is handled by nanofiltration membrane, and filtered fluid enters high ammonia nitrogen with the waste water after the ion exchange resin treatment together
Storage of waste water tank (5)；
(2) waste water high ammonia-nitrogen wastewater holding vessel (5) after mixing, into high ammonia-nitrogen wastewater destilling tower (6), temperature 80~
After 90 DEG C are distilled, waste water discharges after carrying out conventional sewage processing；
(3) NH that high ammonia-nitrogen wastewater volatilizees through destilling tower (6)3It is delivered to equipped with anhydrous SrCl2NH3Adsorptive reactor (7), In
NH3Adsorptive reactor (7) generates Sr(NH3)(8-x)Cl2, Sr(NH3)(8-x)Cl2Through material conveying pipe to (8), Sr(NH3)(8-x)
Cl2It is decomposed in (8) high temperature and produces NH3, produced NH3While the NO with collection automobilexIt carries out reaction and generates N2And H2O, final N2Row
It is put into atmosphere.
In the preferred embodiments of the present invention, in step (1), the treatment process of ion exchange resin be divided into absorption,
Parsing and regeneration, kasugarnycin are poly- as follows in ion exchange resin exchange process step:
1. adsorption process R-SO3H + Kas+→ R-SO3Kas +H+ ；
2. resolving R-SO3Kas + NH4 +→R-SO3NH4 +Kas+；
3. regenerative process R-SO3NH4 + NaOH → R-SO3Na +NH4OH, R-SO3Na + H+→ R-SO3H+Na+；
Wherein,
1. adsorption process parameter: kasugarnycin acidifying solution pH2.5~3.5,28~35 DEG C of adsorption temp, tank pressure for 0.03~
0.05MPa, flow of filtrate 2.0m3/h；
2. resolving parameter: NH4Cl mass percent 3.5% parses 1.2~1.5m of flow3/h；
3. regenerative process parameter: concentration of hydrochloric acid 2.0mol/L, naoh concentration 2.0mol/L, 2.0~3.0m of regenerant flow3/
H, reproduction time 4h.
Further, the waste water obtained after ion exchange contains NH4Cl, hydrochloric acid and sodium hydroxide, pH be 3.5~
6.5, NH45120~6150mg/L of-N concentration 1450~1658mg/L, COD concentration.
In the preferred embodiments of the present invention, in step (2), with polysulfones nanofiltration membrane kasugarnycin exchange liquid by
Nanofiltration membrane is handled, and filtration parameter is as follows: 1.0~1.5MPa of membrane pressure, and the flow through nanofiltration membrane is 32.5L/hm2, cut
Stay liquid is spray-dried to prepare kasugarnycin raw medicine, filtered fluid enters together with the waste water after the ion exchange resin treatment
High ammonia-nitrogen wastewater holding vessel.
In the preferred embodiments of the present invention, in step (2), the NO of Engine Exhaust EmissionxWith Sr(NH3)8Cl2
Reaction temperature be 100-300 DEG C, preferably 200 DEG C.
Wherein, the chemical reaction that step (3) occurs is as follows:
8NH3+SrCl2→ Sr(NH3)(8-x)Cl2
Sr(NH3)(8-x)Cl2+NOx→SrCl2+H2O+N。
In the preferred embodiments of the present invention, SrCl2It can be with the NH of entrance3It reacts and generates Sr(NH3)(8-x)
Cl2, Sr(NH3)(8-x)Cl2It is decomposed at a temperature of 100~300 DEG C and generates NH3, NH3Finally with the NO of Engine Exhaust EmissionxInstead
N should be generated2And H2O。
Compared with prior art, the invention has the following advantages:
1. the ammonia nitrogen in the high ammonia-nitrogen wastewater generated using microbial fermentation, especially streptomyces microaureus fermentation liquid are being separated
With in purification process produce high ammonia-nitrogen wastewater in ammonia nitrogen, to restore automobile NOx, also high ammonia-nitrogen wastewater destilling tower (6 of Fig. 1) are received
Collect ammonia, ammonia and anhydrous SrCl2It reacts and generates Sr(NH3)(8-x)Cl2, Sr(NH3)(8-x)Cl2, in 200~400 DEG C of high temperature
Lower decomposition generates NH3, NH3Finally with the NO of Engine Exhaust EmissionxReaction generates N2And H2O。
2. the present invention produces NH with decomposition under urea high temperature3, the NH that then decomposes3Restore NOxIt compares, is more suitable for low temperature environment
With overcome urea pyrolytic produce this disadvantage of cyanuric acid plug nozzle.
3. the present invention reduces microbial fermentation enterprise because further collecting to ammonia nitrogen in high density and processing pressure, a more step
It reduces ammonia and spills into the pollution that air causes ambient atmosphere environment.
4. the NO of the ammonia reduction motor vehicle emission for the high ammonia-nitrogen wastewater that the present invention is generated using microbial fermentationx, simple side
Just, main indicator is clearly controllable.
Detailed description of the invention
It is described further with reference to the accompanying drawing:
Fig. 1 is that microbial fermentation produces high ammonia-nitrogen wastewater and vehicle exhaust NOxCoupling processing device；
Wherein, 1, polysulfones nanofiltration membrane liquid；2, ceramic membrane filtration liquid；3, nanofiltration membrane；4, ion exchange resin；5, high ammonia nitrogen is useless
Water store tank；6, high ammonia-nitrogen wastewater destilling tower；7,NH3Adsorptive reactor；8,NH3Restore NOxReactor
Fig. 2 is the standard curve of ammonia nitrogen；
Fig. 3 is the process flow chart for producing kasugarnycin raw medicine；
Fig. 4 is mixing ammonia nitrogen waste water through Rotary Evaporators treated water sample.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, without structure
At limitation of the present invention.
The technological means of use is as follows:
1, potassium dichromate method measurement microbial fermentation produces the COD method of ammonia nitrogen waste water
1.1 Method And Principles:
In strongly acidic solution, excessive potassium bichromate standard solution is added, is heated to reflux, aoxidizes the reducing substances in water,
Excessive potassium bichromate makees indicator with ferroin reagent, with iron ammonium sulfate standard solution residual titration, according to consumed weight
Potassium chromate standard solution amount calculates the COD in water sample；
Cr2O7 2-+14H++6e→2Cr3++7H2O (oxidation of water sample)
Cr2O7 2-+14H++6Fe+3→2Cr3++6Fe+2+7H2O (titration)
Fe+2+ reagent (ferrous spirit indicator) → bronzing (terminal)
1.2 determination step
1) water sample for taking 20.00 mL uniformly mixed is placed in the reflux conical flask of 250mL ground, and 0.4g mercuric sulfate is added to disappear
The influence of removing chloride is added 10.00mL potassium bichromate standard solution and several beades or zeolite is added, shakes and mix, then delay
Slow sulfuric acid-silver sulfate solution that 30mL is added, covers condenser pipe top with small beaker, in adjustable electric stove heating boiling reflux 2h.
2) after cooling, condensation tube wall is rinsed with 90mL water, removes conical flask.Overall solution volume must not be less than 140mL.
3) after solution cools down once again, add 3 drops (about 150 μ L) ferroin indicator solution, with iron ammonium sulfate standard solution
Titration, the color of solution is terminal through blue-green to bronzing by yellow, records the dosage of iron ammonium sulfate standard solution.
4) it takes 20.00mL double distilled water to replace water sample, does blank assay by same operation.Sulfuric acid when record titration blank
The dosage of ferrous ammonium standard solution.
1.3 results calculate
2, the test method of ammonia nitrogen
2.1 Method And Principle
When ammonia nitrogen is with free state (NH3) or ammonia radical ion (NH4 +- N) etc. the generation that can react with nessler reagent in the presence of forms
Light red brown colloidal state complex compound, the coloration and ammonia-nitrogen content of the complex compound are proportional, and extinction is measured at 420 nm of Yu Bochang
Degree, can calculate its content.
The pretreatment of 2.2 samples
1) chlorine residue is removed
Chlorine residue in water sample can form chloramines interference measurement with ammonia nitrogen and go as a result, may be typically added suitable hypo solution
It removes.Finally examine whether chlorine residue eliminates with starch-kalium iodide test paper.
2) flocculation sedimentation
Be added 1 mL solution of zinc sulfate in every 100 mL water sample, 0.1~0.2 mL sodium hydroxide solution is added adjust pH to
10.It mixes to stand and is allowed to precipitate, incline and supernatant is taken to analyze.If flocculation sedimentation effect is bad, can with no ammonium hydroxide it is flushed in
Fast filter paper filtering, discards 20 mL of primary filtrate.
2.3 analytical procedure
1) drafting of calibration curve
0.00,0.50,1.00,2.00,4.00,6.00,8.00 and 10.00mL ammonia nitrogen standard is added using solution respectively
Into 8 50mL colorimetric cylinders, corresponding to ammonia-nitrogen content be respectively 0.0,5.0,10.0,20.0,40.0,60.0,80.0
With 100 μ g, it is diluted with water to graticule.1.0 mL potassium sodium tartrate solutions are added, shake up, add 1.5 mL of nessler reagent.
After standing 10 min, at 420 nm of wavelength, using with 10 mm cuvettes, reference is made with no ammonium hydroxide, measures absorbance.With
Its corresponding ammonia-nitrogen content (μ g) is abscissa, and the absorbance after blank correction is ordinate, draws the calibration curve of ammonia nitrogen.
2) sample measures
If the mass concentration of ammonia nitrogen is higher than determination of the upper limit in pretreated 50 mL(water sample of water sample of learning from else's experience, suitable multiple should be taken
Dilution, determination step are same as above).
3) blank test
Water replaces water sample, carries out pre-treatment and measurement by the step identical as sample.
2.4 results calculate
The mass concentration of ammonia nitrogen is calculated as follows in water:
3, the measurement of the kasugarnycin of the waste water in kasugarnycin separation of fermentative broth purification process and waste residue
The reagent is as follows:
Acetonitrile: chromatographically pure；Water: secondary distilled water is newly steamed；Kasugamycin hydrochloride hydrate standard specimen: known quality score >=
80.0%。
The instrument is as follows:
High performance liquid chromatograph: there is Variable wavelength UV detector；Chromatographic data processor；Chromatographic column: 150mm × 3.9mm
(id) stainless steel chromatographic column, Waters symetryshield RP18,5 μm of partial size；Microsyringe: 50 μ L.
High performance liquid chromatography operating condition is as follows:
Mobile phase: 0.5% lauryl sodium sulfate aqueous solution: acetonitrile=80: 20(v/v), it is 2.5 with phosphoric acid tune pH value.
Flow velocity: 1.0mL/min；Detection wavelength: 210nm；Temperature: 25 DEG C；Sampling volume: 10 μ L；Retention time: spring thunder
Mycin about 10.7min.
It calculates:
The area of kasugarnycin in two needle standard specimen solutions before and after the two needle sample solutions and sample that measure is averaged respectively,
The mass fraction ω of kasugarnycin in sample1(%) is calculated by formula (1):
In formula: A 1 In standard specimen solution, the average value of kasugarnycin peak area；
A 2 In sample solution, the average value of kasugarnycin peak area；
m 1 The quality of kasugarnycin standard specimen, unit are gram (g)；
m 2 The quality of sample, unit are gram (g)；
The mass fraction (%) of kasugarnycin in ω-- standard specimen.
Embodiment 1
Small golden amount mold fermentation technique uses Batch fermentation, and specific zymotechnique process is as shown in figure 3, from process flow chart
3 it is found that ammonia nitrogen waste water initially with ammonium ion (NH4 +) it is primarily present ceramic membrane filtration liquid, ion exchange resin waste liquid and nanofiltration membrane
Waste liquid is filtered, wherein wastewater flow rate is that (ceramic membrane is useless for ion exchange resin waste liquid measure > nanofiltration membrane waste liquid > ceramic membrane filtration liquid
Water is mainly cleaning solution, and what it is through ceramic membrane interception is kasugarnycin waste residue), three-level after the total 189h of streptomyces microaureus Batch fermentation
Tank puts tank (30 tons), puts tank liquid after oxalic acid is acidified, successively by ceramic membrane filter, ion exchange resin, nanofiltration membrane and last
Spray drying.The content of COD, ammonia nitrogen and kasugarnycin in the waste water of each process section are shown in Table shown in 1.1.
Ammonia nitrogen, COD and kasugarnycin content of the 1.1 streptomyces microaureus fermentation liquid of table in different isolation and purification process sections
Situation of change
It can be seen that successively acidified kasugarnycin fermentation liquid, ceramic membrane filter, ion exchange resin and nanofiltration from table 1.1
In membrane filtration processes, kasugarnycin content is the 108925 μ g/mL for becoming nanofiltration section from initial 12560 μ g/mL of fermentation liquid, is received
Rate is 90.3%, and kasugarnycin fermentation liquid produced ammonia nitrogen in waste water and COD highest process section after isolation and purification technique are ion friendship
Resin section and nanofiltration membrane section are changed, ion exchange resin section waste water and the produced high ammonia-nitrogen wastewater of nanofiltration section are pumped through pipeline
Enter to high ammonia-nitrogen wastewater storage tank.
Embodiment 2
The filtrated stock of ion exchange is the kasugarnycin fermentation liquid through ceramic membrane filter, and ion exchange process is divided into absorption, solution
Analysis and regeneration, kasugarnycin are poly- as follows in ion exchange resin exchange process step: 1. adsorption process R-SO3H + Kas+→ R-SO3Kas
+H+ ；2. resolving R-SO3Kas + NH4 +→R-SO3NH4 +Kas+；3. regenerative process R-SO3NH4 + NaOH → R-
SO3Na +NH4OH, R-SO3Na + H+→ R-SO3H+Na+, wherein adsorption process parameter: 1. kasugarnycin acidifying solution pH2.5~
3.5,28~35 DEG C of adsorption temp, tank pressure is 0.03~0.05MPa, flow of filtrate 2.0m3/h；2. resolving parameter: NH4Cl
Mass percent 3.5% parses 1.2~1.5m of flow3/h；(3) regenerative process parameter: concentration of hydrochloric acid 2.0mol/L, sodium hydroxide
Concentration 2.0mol/L, 2.0~3.0m of regenerant flow3/ h, reproduction time 4h (30 tons of ion exchange mother liquors), through ceramic membrane filtration liquid
Kasugarnycin fermentation liquid after ion exchange, produce high ammonia-nitrogen wastewater amount be 60 tons；Ion exchange liquid is with polyether sulfone filtering film mistake
Filter gained filter liquor is high ammonia-nitrogen wastewater, and wastewater flow rate is 20 tons；Concrete outcome is shown in Table 2.1.
The ammonia nitrogen concentration and COD concentration of 2.1 ammonia nitrogen waste water storage tank of table
From table 2.1 it is found that the concentration of ammonia nitrogen waste water storage tank ammonia nitrogen is 1532mg/L, COD 5512.5mg/L, kasugarnycin content
689.25mg/L, ammonia nitrogen amounts to 122.56kg, and the ammonia nitrogen used is 150kg, then 27.44kg largely has kasugarnycin
There are ceramic membrane cleaning solution and nanofiltration liquid, the ammonia nitrogen of ammonia nitrogen waste water storage tank accounts for entire ammonia nitrogen usage amount for waste residue and fraction
81.71%。
Embodiment 3
It stays to verify steaming and ammonia nitrogen is removed well, taking three samples of 1L waste water from ammonia nitrogen waste water storage tank, (sample opening is put
Set), three samples are distilled (temperature is 60-80 DEG C) in Rotary Evaporators for three days on end, and concrete outcome is shown in Fig. 4 and table as follows
3.1。
The ammonia nitrogen and COD concentration of 3.1 rotary evaporation of table change
From table Fig. 4 and table 3.1 it is found that distillation can substantially reduce the ammonia nitrogen of original mixed high ammonia-nitrogen wastewater, it is within removal rate the 1st day
87.5%, the 2nd day be 86.4% and the 3rd day 83%, the 1st day Residual liquid 101.5mL after distillation, 99.5mL and the 3rd day the 2nd day
99.3mL distills the process that only concentration is influenced on COD.
Embodiment 4
The high ammonia-nitrogen wastewater of ammonia nitrogen waste water storage tank is pumped into MVR reactor, and MVR installed power is 57KW, steam consumption
0.38t/h, processing wastewater flow rate are 10t/h, and the ammonia of distillation is input to NH through pipeline3Adsorptive reactor (7), according to 8NH3+
SrCl2→ Sr(NH3)(8-x)Cl2, it is 108.12kg that 80 tons of waste water collect ammonia altogether, and mineralized nitrogen is at the conversion ratio of ammonia
88.2%。
Embodiment 5
In order to further investigate SrCl2With NH3It adsorbs and combines situation, strontium chloride and strontium chloride in silochrom or AI2O3Carrier
At 300 DEG C, 500 DEG C and 600 DEG C of Suitable Roast Temperature of upper dispersion, then in closed reactor (the reactor initial vacuum,
Since the ammonia of high pressure ammonia tank flows into the closed reactor, start 1.0Mpa, 1.5Mpa and 2.0Mpa, silica gel or AI2O3: chlorine
Change strontium=0.5, reaction temperature is 35 DEG C), high pressure ammonia is passed through by pressure reducing valve and supports a certain amount of SrCl equipped with different carriers2
Adsorption sample, be packed into the SiO of different-grain diameter2Or AI2O3The SrCl supported2, the SrCl under 35 DEG C and different pressures2To dried
Ammonia combination situation, concrete outcome is shown in Table 5.1.
Table 5.1TiO2Support the SrCl of different-grain diameter2Under different pressure and temperature conditions to NH3Combination situation
From table 5.1 it is found that the SiO of the same particle size of 500 DEG C of roastings2Or AI2O3Support SrCl2Ammonia is adsorbed at various pressures
Amount range is 0.37~0.46g/g, the SiO of same particle size2Or AI2O3Support SrCl2To NH3Adsorbance with ammonia pressure
It increases and increases, but with pressure increase, adsorbance increasing degree is to slow down gradually；The smaller SiO of partial size2Or AI2O3It supports
SrCl2To NH under identical maturing temperature and uniform pressure3Adsorbance be increased；The SiO of same particle size under 0.7Mpa2
Or AI2O3Support SrCl2To NH3Adsorbance be increased to 500 DEG C with ammonia pressure as highest, and in 400 DEG C and 600 DEG C
It is to reduce, wherein 600 DEG C of adsorbances are minimum, the reason is that 500 DEG C of roasting sample Monolayer Dispersions are good, at 600 DEG C
SrCl2Crystal phase is inhomogenous, causes the adsorbance to ammonia on the low side.Under mutually synthermal different pressures or the roasting of uniform pressure difference is warm
Under degree, the SrCl of 100 ± 15nm of partial size2To ammonia gas absorption amount and same particle size SiO2Or AI2O3Support SrCl2Absorption to ammonia
It measures similar.
Embodiment 6
In order to further investigate the Sr(NH under different temperatures3)(8-x)Cl2With the NO in automobile engine exhaust pipexResponse situation
And to NOxRemoval rate, concrete outcome are shown in Table 6.1.
Sr(NH under 6.1 different temperatures of table3)(8-x)Cl2With the NO in automobile engine exhaust pipeXThe case where removal rate (%)
From table 6.1 it is found that the SiO of different-grain diameter2Or AI2O3Support SrCl2Adsorption saturation strontium chloride adsorbs NH3Reaction system
With NOxReaction is and Sr(NH3)(8-x)Cl2Desorption has a relationship, and the smaller desorption of partial size is more difficult, at identical temperature partial size it is smaller with
NOxTo NO after reactionXRemoval rate be reduce；The SiO of same particle size under different temperatures2Or AI2O3Support SrCl2It is inhaled with saturation
Attached NH3Strontium chloride reaction system is at 200 DEG C, SrCl2(100 ± 15nm of partial size) is to NOxRemoval rate be three's temperature in most
It is high；The SrCl of saturation type absorption ammonia2、SiO2Or AI2O3Support SrCl2, 300 DEG C to NOxRemoval rate is minimum.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
The change or replacement expected without creative work, should be covered by the protection scope of the present invention.Therefore, of the invention
Protection scope should be determined by the scope of protection defined in the claims.
Claims (9)
1. a kind of microbial fermentation produces high ammonia-nitrogen wastewater and automobile NOxThe device of coupling processing, which is characterized in that the device
Including nanofiltration membrane (3), ion exchange resin (4), high ammonia-nitrogen wastewater holding vessel (5), high ammonia-nitrogen wastewater destilling tower (6), NH3Absorption
Reactor (7) and NH3Restore NOxReactor (8), wherein the kasugarnycin fermentation liquid through ceramic membrane filter is by ion exchange resin
(4) it handles, is handled with polysulfones nanofiltration membrane kasugarnycin exchange liquid by nanofiltration membrane (3), filtered fluid is with the ion
Treated that waste water enters high ammonia-nitrogen wastewater holding vessel (5) together for exchanger resin, then passes sequentially through high ammonia-nitrogen wastewater destilling tower
(6), ammonia and SrCl2The reactor (7) and NO of reactionxReduction reactor (8).
2. the apparatus according to claim 1, which is characterized in that the ion exchange resin is preferably cation (H+Type)
Ion exchange resin.
3. the apparatus according to claim 1, which is characterized in that the high ammonia-nitrogen wastewater destilling tower (6) is MVR reaction
Device.
4. a kind of microbial fermentation produces high ammonia-nitrogen wastewater and automobile NOxThe method of coupling processing, which is characterized in that including following step
It is rapid:
(1) the kasugarnycin fermentation liquid through ceramic membrane filter is mould with polysulfones nanofiltration membrane spring thunder by ion exchange resin treatment
Element exchange liquid is handled by nanofiltration membrane, and filtered fluid enters high ammonia nitrogen with the waste water after the ion exchange resin treatment together
Storage of waste water tank；
(2) waste water high ammonia-nitrogen wastewater holding vessel after mixing, into high ammonia-nitrogen wastewater destilling tower, 80~90 DEG C of temperature into
After row distillation, waste water discharges after carrying out conventional sewage processing；
(3) NH that high ammonia-nitrogen wastewater volatilizees through destilling tower (6)3It is delivered to equipped with anhydrous SrCl2NH3Adsorptive reactor (7), In
NH3Adsorptive reactor (7) generates Sr(NH3)(8-x)Cl2, Sr(NH3)(8-x)Cl2Through material conveying pipe to (8), Sr(NH3)(8-x)
Cl2It is decomposed in (8) high temperature and produces NH3, produced NH3While the NO with collection automobilexIt carries out reaction and generates N2And H2O, final N2Row
It is put into atmosphere.
5. according to the method described in claim 4, it is characterized in that, the treatment process of ion exchange resin is divided into step (1)
Absorption, parsing and regeneration, kasugarnycin are poly- as follows in ion exchange resin exchange process step:
1. adsorption process R-SO3H + Kas+ → R-SO3Kas +H+ ；
2. resolving R-SO3Kas + NH4 + →R-SO3NH4 +Kas+；
3. regenerative process R-SO3NH4 + NaOH → R-SO3Na +NH4OH, R-SO3Na + H+ → R-SO3H+Na+；
Wherein,
1. adsorption process parameter: kasugarnycin acidifying solution pH2.5~3.5,28~35 DEG C of adsorption temp, tank pressure for 0.03~
0.05MPa, flow of filtrate 2.0m3/h；
2. resolving parameter: NH4Cl mass percent 3.5% parses 1.2~1.5m of flow3/h；
3. regenerative process parameter: concentration of hydrochloric acid 2.0mol/L, naoh concentration 2.0mol/L, 2.0~3.0m of regenerant flow3/ h,
Reproduction time 4h.
6. according to the method described in claim 4, it is characterized in that, ceramic membrane filtration liquid produced waste water contains after ion exchange
NH4Cl, hydrochloric acid and sodium hydroxide, pH are 3.5~6.5, NH4- N concentration 1450~1658mg/L, COD concentration 5120~
6150mg/L。
7. according to the method described in claim 4, it is characterized in that, being handed in step (2) with polysulfones nanofiltration membrane kasugarnycin
Change liquid to be handled by nanofiltration membrane, filtration parameter is as follows: 1.0~1.5MPa of membrane pressure, the flow through nanofiltration membrane are 32.5/h
m2, trapped fluid is spray-dried to prepare kasugarnycin raw medicine, and filtered fluid is with the waste water one after the ion exchange resin treatment
It is same to enter high ammonia-nitrogen wastewater holding vessel.
8. according to the method described in claim 4, it is characterized in that, in step (2), Engine Exhaust Emission NOxTemperature it is usual
It is 100-300 DEG C.
9. according to the method described in claim 4, it is characterized in that, SrCl2It can be with the NH of entrance3It reacts and generates Sr
(NH3)(8-x)Cl2, Sr(NH3)(8-x)Cl2It is decomposed under 100-300 DEG C of high temperature and generates NH3, NH3Finally and Engine Exhaust Emission
NOx reaction generate N2And H2O。
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