CN106990184A - A kind of printing and dyeing sludge inorganic constituents analogies and its application - Google Patents
A kind of printing and dyeing sludge inorganic constituents analogies and its application Download PDFInfo
- Publication number
- CN106990184A CN106990184A CN201710321150.6A CN201710321150A CN106990184A CN 106990184 A CN106990184 A CN 106990184A CN 201710321150 A CN201710321150 A CN 201710321150A CN 106990184 A CN106990184 A CN 106990184A
- Authority
- CN
- China
- Prior art keywords
- printing
- analogies
- sludge
- dyeing sludge
- dyeing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/05—Investigating materials by wave or particle radiation by diffraction, scatter or reflection
- G01N2223/056—Investigating materials by wave or particle radiation by diffraction, scatter or reflection diffraction
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
- G01N2223/076—X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/10—Different kinds of radiation or particles
- G01N2223/101—Different kinds of radiation or particles electromagnetic radiation
- G01N2223/1016—X-ray
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Coloring (AREA)
Abstract
The invention belongs to chemical analysis field, more particularly to a kind of printing and dyeing sludge inorganic constituents analogies and its application.The printing and dyeing sludge inorganic constituents analogies that the present invention is provided are prepared in accordance with the following methods：A), flocculant and calcium compound are mixed in a solvent, obtain the mixed liquor that pH value is 6.5~7.5；The flocculant includes aluminium polychloride or bodied ferric sulfate；The calcium compound includes calcium hydroxide and/or calcium oxide；B), the mixed liquor carries out separation of solid and liquid and drying, obtains printing and dyeing sludge inorganic constituents analogies.The present invention prepares printing and dyeing sludge inorganic constituents analogies with flocculant and calcium compound, test result indicates that the analogies and the consistent appearance of actual printing and dyeing sludge inorganic constituents, composition are close.Therefore, the printing and dyeing sludge simulated system being made up of printing and dyeing sludge inorganic constituents analogies, water and the organic principle to be analyzed can be used for degradative pathway and catabolite of certain organic matter in printing and dyeing sludge of analyzing and researching.
Description
Technical field
The invention belongs to chemical analysis field, more particularly to a kind of printing and dyeing sludge inorganic constituents analogies and its application.
Background technology
Dyeing waste water is containing Recalcitrant chemicals such as a large amount of dyestuffs, auxiliary agent and detergent, and intractability is big, and it is main undegraded
Shift and be enriched in sludge in part.Annual report is counted according to Chinese environmental in 2014, national printing and dyeing sludge yield is about 4,900,000 tons
(based on moisture content 80%) is in addition to municipal sludge, it is necessary to the maximum industrial sludge of the quantity for carrying out external treatment disposal.Early stage
Research shows, ∑ in the printing and dyeing sludge of the typical printing and dyeing enterprise in 10, Pearl River Delta16PAHs average value 6,386ng g-1, toxicity maximum
BaP average value 140.51ng g-1, mainly based on 3 rings and 4 ring PAHs；14 kinds of μ g of aromatic amine average 25 in printing and dyeing sludge
g-1, based on mono-cyclic aromatic amine, wherein 2- methoxyl groups -5- methylanilines and 2- amino -4- nitrotoleune content highests.Many cyclophanes
Hydrocarbon and aromatic amine are the principal character pollutants of printing and dyeing sludge, respectively with moderate carcinogenic risk and high accumulation eco-toxicity wind
Danger.Therefore, it is to reduce its environmental risk effectively to remove the persistent organic pollutants such as polycyclic aromatic hydrocarbon, aromatic amine in printing and dyeing sludge
It is crucial.
In recent years, physical-chemical process is organic in particular with difficult degradation in high-level oxidation technology degradable solid discarded object matrix
The research of thing gradually increases, such as Fenton methods, electrochemical process, Ozone and ultrasonic method.For bioanalysis, depth oxygen
Change method degradation of organic substances is simple to operate, reaction speed is fast and degradation efficiency is high.But some way is evaluated if appropriate for for handling
During organic matter, in addition to considering the removal effect of organic matter, it is also contemplated that the toxicity of its reaction product.Organic matter is in complex system
Can be with the substance reaction of other in surrounding medium in degradation process so that the toxicity of catabolite changes, and what is had can make
Originally the organic matter without mutagenicity has a mutagenicity, and have there is adverse effect.Therefore, it is organic in printing and dyeing sludge system
Intermediate product after thing is handled through high-level oxidation technology still needs to further further investigation.But a kind of suitable dirt is difficult to find that at present
Mud simulated system studies degraded and conversion process of the organic pollution in sludge.
The content of the invention
In view of this, it is an object of the invention to provide a kind of printing and dyeing sludge inorganic constituents analogies and its application, at this
Invent to add in the printing and dyeing sludge inorganic constituents analogies provided after water and organic principle to be analyzed and can obtain printing and dyeing sludge
Simulated system, the system can be used for degraded situation of the research organic matter in printing and dyeing sludge.
The invention provides a kind of printing and dyeing sludge inorganic constituents analogies, prepare in accordance with the following methods：
A), flocculant and calcium compound are mixed in a solvent, obtain the mixed liquor that pH value is 6.5~7.5；
The flocculant includes aluminium polychloride or bodied ferric sulfate；The calcium compound includes calcium hydroxide and/or oxygen
Change calcium；
B), the mixed liquor carries out separation of solid and liquid, and isolated solid formation is dried afterwards, printing and dyeing sludge is obtained
Inorganic constituents analogies.
It is preferred that, the step a) is specifically included：
A1), flocculant and solvent are mixed, flocculant solution is obtained；
A2 calcium compound), is added into the flocculant solution, stops addition after solution ph is 6.5~7.5, obtains
To mixed liquor.
It is preferred that, the concentration of the flocculant solution is 3~10wt%.
It is preferred that, in step b), the mode of the drying is lyophilized.
The invention provides a kind of printing and dyeing sludge analogies, including printing and dyeing sludge organic principle, water and above-mentioned technical proposal
Described printing and dyeing sludge inorganic constituents analogies.
It is preferred that, the mass ratioes of printing and dyeing sludge organic principle and printing and dyeing sludge the inorganic constituents analogies for (10~
100)：(1000~10000)；
The moisture content of the printing and dyeing sludge analogies is 90~99wt%.
It is preferred that, the printing and dyeing sludge organic principle includes polycyclic aromatic hydrocarbon and/or aromatic amine.
A kind of analysis method for situation of being degraded the invention provides organic matter in printing and dyeing sludge, comprises the following steps：
A the printing and dyeing sludge inorganic constituents analogies mixing described in organic matter, water and above-mentioned technical proposal), is analysed to, is obtained
To printing and dyeing sludge analogies；
B oxidative degradation, printing and dyeing sludge analogies after being degraded), are carried out to the printing and dyeing sludge analogies；
C composition detection), is carried out to printing and dyeing sludge analogies after the degraded, testing result is obtained.
It is preferred that, step B) in, the mode of the oxidative degradation is：Oxidation is added in the printing and dyeing sludge analogies
Agent.
It is preferred that, step B) in, the oxidative degradation is carried out in the presence of ultrasonic wave.
Compared with prior art, the invention provides a kind of printing and dyeing sludge inorganic constituents analogies and its application.The present invention
The printing and dyeing sludge inorganic constituents analogies of offer are prepared in accordance with the following methods：A), flocculant and calcium compound be in a solvent
Mixing, obtains the mixed liquor that pH value is 6.5~7.5；The flocculant includes aluminium polychloride or bodied ferric sulfate；The calcification
Compound includes calcium hydroxide and/or calcium oxide；B), the mixed liquor carries out separation of solid and liquid, afterwards by isolated solid formation
It is dried, obtains printing and dyeing sludge inorganic constituents analogies.The present invention prepares printing and dyeing sludge with flocculant and calcium compound
Inorganic constituents analogies, test result indicates that the analogies and the consistent appearance of actual printing and dyeing sludge inorganic constituents, composition are close.
Therefore, the printing and dyeing sludge simulated system being made up of printing and dyeing sludge inorganic constituents analogies, water and the organic principle to be analyzed can use
In degradative pathway and catabolite of certain organic matter in printing and dyeing sludge of analyzing and researching.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is the XRF analysis figure for the 1st printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Fig. 2 is the XRF analysis figure for the 2nd printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Fig. 3 is the XRF analysis figure for the 3rd printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Fig. 4 is the XRF analysis figure for the 4th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Fig. 5 is the XRF analysis figure for the 5th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Fig. 6 is the XRF analysis figure for the 6th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Fig. 7 is the XRD spectra for six printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Fig. 8 is the SEM figures for the 1st printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Fig. 9 is the EDS analysis results for the 1st printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Figure 10 is the SEM figures for the 2nd printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Figure 11 is the EDS analysis results for the 2nd printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Figure 12 is the SEM figures for the 3rd printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Figure 13 is the EDS analysis results for the 3rd printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Figure 14 is the SEM figures for the 4th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Figure 15 is the EDS analysis results for the 4th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Figure 16 is the SEM figures for the 5th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Figure 17 is the EDS analysis results for the 5th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Figure 18 is the SEM figures for the 6th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Figure 19 is the EDS analysis results for the 6th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；
Figure 20 is the XRF analysis figure for the inorganic constituents analogies of sludge containing PFS that the embodiment of the present invention 2 is provided；
Figure 21 is the XRF analysis figure for the inorganic constituents analogies of sludge containing PAC that the embodiment of the present invention 2 is provided；
Figure 22 is the XRD spectra for the sludge inorganic constituents analogies that the embodiment of the present invention 2 is provided；
Figure 23 is the SEM figures for the inorganic constituents analogies of sludge containing PFS that the embodiment of the present invention 2 is provided；
Figure 24 is the EDS analysis results for the inorganic constituents analogies of sludge containing PFS that the embodiment of the present invention 2 is provided；
Figure 25 is the SEM figures for the inorganic constituents analogies of sludge containing PAC that the embodiment of the present invention 2 is provided；
Figure 26 is the EDS analysis results for the inorganic constituents analogies of sludge containing PAC that the embodiment of the present invention 2 is provided.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
The invention provides a kind of printing and dyeing sludge inorganic constituents analogies, prepare in accordance with the following methods：
A), flocculant and calcium compound are mixed in a solvent, obtain the mixed liquor that pH value is 6.5~7.5；
The flocculant includes aluminium polychloride or bodied ferric sulfate；The calcium compound includes calcium hydroxide and/or oxygen
Change calcium；
B), the mixed liquor carries out separation of solid and liquid, and isolated solid formation is dried afterwards, printing and dyeing sludge is obtained
Inorganic constituents analogies.
In the present invention, to obtain printing and dyeing sludge inorganic constituents analogies, first have to flocculant and calcium compound molten
Mixed in agent.Wherein, the flocculant includes aluminium polychloride (abbreviation PAC) or bodied ferric sulfate (abbreviation PFS)；The polymerization
The chlorination aluminium content of aluminium chloride preferably >=35wt%, concretely 36wt%；The basicity of the aluminium polychloride is preferably 40
~85%, concretely 50%；The water of the aluminium polychloride not solubility content preferably≤0.3wt%；The aluminium polychloride
PH value (the 10g/L aqueous solution) be preferably 3.5~4.0, concretely 4.3；The sulfuric acid iron content of the bodied ferric sulfate is preferred
For 20~21wt%；The basicity of the bodied ferric sulfate is preferably 9~14%, and concretely 11%；The bodied ferric sulfate
PH value (the 10g/L aqueous solution) be preferably 2.0~3.0, concretely 2.5；The calcium compound includes calcium hydroxide and/or oxygen
Change calcium；The solvent is preferably water.In mixed process, flocculant and calcium compound react in a solvent, obtain containing flocculation
The mixed liquor of body.The pH value of the mixed liquor is 6.5~7.5, preferably 7.In the present invention, by adjusting flocculant, calcification
The consumption of compound and solvent adjusts the pH value of mixed liquor.
In one embodiment that the present invention is provided, the mixed liquor is preferably prepared in the following manner：
A1), flocculant and solvent are mixed, flocculant solution is obtained；
A2 calcium compound), is added into the flocculant solution, stops addition after solution ph is 6.5~7.5, obtains
To mixed liquor.
In the above-mentioned preparation method that the present invention is provided, the concentration of the flocculant solution is preferably 3~10wt%, specifically
Can be 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%；The addition manner of the calcium compound
Calcium compound is preferably configured to calcium compound solution, is then added dropwise in the flocculant solution.
Obtain after the mixed liquor, carry out separation of solid and liquid to the mixed liquor, the mode of the separation of solid and liquid be preferably from
The heart is separated.The solid formation of separation of solid and liquid is dried afterwards, printing and dyeing sludge inorganic constituents analogies are obtained.Wherein, it is described dry
Dry mode is preferably lyophilized.
The present invention prepares printing and dyeing sludge inorganic constituents analogies, the analogies and reality with flocculant and calcium compound
The consistent appearance of printing and dyeing sludge inorganic constituents, composition is close.Therefore, by the printing and dyeing sludge inorganic constituents analogies, water and treat point
The printing and dyeing sludge simulated system of analysis organic principle composition can be used for degraded road of certain organic matter in printing and dyeing sludge of analyzing and researching
Footpath and catabolite.
The invention provides a kind of printing and dyeing sludge analogies, including printing and dyeing sludge organic principle, water and above-mentioned technical proposal
Described printing and dyeing sludge inorganic constituents analogies.
The printing and dyeing sludge analogies that the present invention is provided include printing and dyeing sludge organic principle, water and the printing and dyeing sludge it is inorganic into
Divide analogies.Wherein, the printing and dyeing sludge organic principle includes but is not limited to polycyclic aromatic hydrocarbon and/or aromatic amine, the aromatic amine
Concretely 4,4 '-diaminodiphenyl-methane (abbreviation DDM)；The printing and dyeing sludge organic principle and printing and dyeing sludge inorganic constituents
The mass ratio of analogies is preferably (10~100)：(1000~10000), concretely 20：5000；The printing and dyeing sludge simulation
The moisture content of thing is preferably 90~99wt%, concretely 98wt%.
The printing and dyeing sludge analogies that the present invention is provided are similar to actual printing and dyeing sludge composition, available for analysis and research organic matter
Degradative pathway and catabolite in printing and dyeing sludge.
A kind of analysis method for situation of being degraded the invention provides organic matter in printing and dyeing sludge, comprises the following steps：
A the simulation printing and dyeing sludge inorganic constituents mixing described in organic matter, water and above-mentioned technical proposal), is analysed to, is obtained
Printing and dyeing sludge analogies；
B oxidative degradation, printing and dyeing sludge analogies after being degraded), are carried out to the printing and dyeing sludge analogies；
C composition detection), is carried out to printing and dyeing sludge analogies after the degraded, testing result is obtained.
In the analogy method that the present invention is provided, printing and dyeing sludge analogies, the printing and dyeing sludge analogies bag are prepared first
Include organic matter to be analyzed, water and the printing and dyeing sludge inorganic constituents analogies.Wherein, the organic matter to be analyzed includes but not limited
In polycyclic aromatic hydrocarbon and/or aromatic amine, the aromatic amine concretely 4,4 '-diaminodiphenyl-methane (abbreviation DDM)；It is described to treat
The mass ratio of analyzing organic substance and printing and dyeing sludge inorganic constituents analogies is preferably (10~100)：(1000~10000), specifically
Can be 20：5000；The moisture content of the printing and dyeing sludge analogies is preferably 90~99wt%, concretely 98wt%.
Afterwards, oxidative degradation is carried out to the printing and dyeing sludge analogies prepared.Wherein, the mode of the oxidative degradation is preferred
To add oxidant in the printing and dyeing sludge analogies；The oxidant is preferably KMnO4；Unit volume printing and dyeing sludge is simulated
KMnO described in thing4Addition be preferably 0.1~0.2mmol/L, concretely 0.12mmol/L.In the present invention, it is described
Oxidative degradation is carried out in the presence of ultrasonic wave, and the ultrasonic density of the ultrasonic wave is preferably 0.3~0.4W/cm3, concretely
0.36W/cm3.In the present invention, it is preferred to be quenched after 3~5min of oxidant reaction is added, it is described that being quenched of using is quenched
Agent is hydroxylamine hydrochloride.After oxidative degradation, printing and dyeing sludge analogies after being degraded.
Obtain after the degraded after printing and dyeing sludge analogies, go-on-go is carried out into printing and dyeing sludge analogies after the degraded
Survey.In one embodiment that the present invention is provided, the composition of printing and dyeing sludge analogies after degraded can be detected in the following ways：
The aqueous phase to printing and dyeing sludge analogies after the degraded is mutually extracted with mud respectively, obtains aqueous phase extract and mud
Phase extract.Wherein, the mode of the aqueous phase extraction is preferably liquid-liquid extraction, and the mode that the mud is mutually extracted is preferably ultrasonic extraction
Take.Obtain after aqueous phase extract and mud phase extract, carry out gas chromatography-mass spectrography (GC-MS) detection to it respectively.At this
In invention, before being detected to the aqueous phase extract and mud phase extract, preferably it is being concentrated and spread out successively
Biochemical treatment.Wherein, the mode of the concentration is preferably that nitrogen blows；The reagent that the aqueous phase extract performs the derivatization processing is preferred
For N, double (trimethylsilyl) trifluoroacetamides of O-, the mud phase extract performs the derivatization the reagent preferably pyrrole of processing
Pyridine.In the present invention, the GC-MS testing conditions are not particularly limited, during GC-MS detection detections, chromatographic column can select HP-
5 type quartz capillary columns (30m × 0.25mm × 0.25 μm)；He may be selected in carrier gas, and carrier gas flux may be selected 1.2mL/min, enter
Sample mouthful temperature may be set to 280 DEG C, and the initial temperature of chromatographic column may be set to 40 DEG C, keep after 2min using heating rate as 6 DEG C/min
Rise to 100 DEG C, then with 10 DEG C/min to 280 DEG C of heating rate；Solvent delay may be set to 4min, and not shunt mode may be selected,
Sample size may be set to 1 μ L；Mass scan range may be selected to be 40~300amu；Electron bombardment energy may be set to 70eV；From
Source temperature may be set to 280 DEG C.
After composition detection is finished, testing result is obtained, then going out organic matter degradation to be analyzed according to Analysis of test results is
Which material.In one embodiment that the present invention is provided, with 4,4 '-diaminodiphenyl-methane as organic matter to be analyzed,
Analysis obtains its catabolite for 3 methoxy 4 hydroxymandelic acid, 3- methoxy-4-phenol methanols, meta-methoxy benzene first
Acid and benzoic acid.
The analysis method that the present invention is provided builds the printing and dyeing sludge analogies similar to actual printing and dyeing sludge composition first, it
Oxidative degradation and constituent analysis are carried out to the printing and dyeing sludge analogies afterwards, so as to obtain certain organic matter in printing and dyeing sludge
Degradative pathway and catabolite.
For the sake of becoming apparent from, it is described in detail below by following examples.
The aluminium polychloride (PAC) used in the following embodiments of the application is by Teng Long material for water treatment Co., Ltd of Gongyi City
There is provided, product designation TL-1023, chlorination aluminium content 36wt%, basicity 50%, water not solubility content 0.03wt%, pH value
(the 10g/L aqueous solution) 4.3；The bodied ferric sulfate (PFS) used is provided by Teng Long material for water treatment Co., Ltd of Gongyi City, product
Code name TL-103, sulfuric acid iron content 21wt%, pH (the 10g/L aqueous solution) 2.5, basicity 11%.
Embodiment 1
The investigation of printing and dyeing sludge system
The printing and dyeing sludge for selecting the 6 printing and dyeing enterprise final process in Guangdong Province is research object, carries out sampling analysis.Printing and dyeing are dirty
After mud is freeze-dried, the Metal Distribution in (XRF) research printing and dyeing sludge is analyzed using X-ray fluorescence spectra, its result is shown in Fig. 1
~6.Fig. 1 is the XRF analysis figure for the 1st printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided, marked as TDP1；Fig. 2 is the present invention
The XRF analysis figure for the 2nd printing and dyeing mill's sludge that embodiment 1 is provided, marked as TDP2；Fig. 3 is that the embodiment of the present invention 1 is provided
The XRF analysis figure of 3 printing and dyeing mill's sludge, marked as TDP3；Fig. 4 is the 4th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided
XRF analysis figure, marked as TDP4；Fig. 5 is the XRF analysis figure for the 5th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided, label
For TDP5；Fig. 6 is the XRF analysis figure for the 6th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided, marked as TDP6.Pass through Fig. 1
~6 as can be seen that TDP 1,2,3,4 main component is that inorganic constituents is Fe2O3, account for 21.22~28.38wt%.It can push away
Disconnected, TDP 1,2,3,4 printing and dyeing sludge is by adding a large amount of generations of flocculant containing Fe during treatment of dyeing wastewater.And TDP
5 and 6 main inorganic composition is Al2O3, 28.09wt% and 34.66wt% are accounted for respectively, and illustrating TDP 5 and 6 printing and dyeing sludge is
By adding a large amount of flocculant generations containing Al during treatment of dyeing wastewater.In TDP 1~3, except Fe2O3Outside, also contain
A small amount of Al2O3The content for containing CaO in CaO, wherein TDP 4 in (3.62~7.51wt%), 6 printing and dyeing mill's sludge is up to
CaO content is 0.29wt% in 25.37wt%, TDP 6, when this adjusts pH from the wastewater treatment flocculation process of different printing and dyeing mills
The CaO of middle addition amount is relevant.Sludge in 6 printing and dyeing mills contains a small amount of SO3, 3.8~14.6wt% is accounted for, may be with life
The industrial chemicals Na commonly used in sulfur dye and printing and dyeing industry during production2SO3It is relevant, loss on ignition (CO3) in 6 sludge
Content in sample at most, accounts for 37.01~53.59wt%.Therefore, the inorganic constituents in printing and dyeing sludge is mainly Fe2O3Or
Al2O3, also containing a small amount of CaO, SO3。
Further using crystal structure analysis of the X-ray diffraction (XRD) to printing and dyeing sludge, its result is shown in Fig. 7.Fig. 7 is this
The XRD spectra for six printing and dyeing mill's sludge that inventive embodiments 1 are provided.As seen in Figure 7, the main component of printing and dyeing sludge is
Impalpable structure (TDP 1,2,5), contains a small amount of AlOOH mineral facies in TDP 3, and CaCO is contained in TDP 3,4,63's
Mineral facies, what these mineral facies may be produced in flocculation or infall process.
Using sweep electron microscope-X-ray micro-zone analysis (SEM-EDS) scanning printing and dyeing sludge overall morphology analysis and
To its local elementary analysis, its result is shown in Fig. 8~19.Fig. 8 is the SEM for the 1st printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided
Figure, Fig. 9 is the EDS analysis results for the 1st printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；Figure 10 is that the embodiment of the present invention 1 is carried
The SEM figures of the 2nd printing and dyeing mill's sludge supplied, Figure 11 is the EDS analyses for the 2nd printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided
As a result；Figure 12 is the SEM figures for the 3rd printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided, and Figure 13 is that the embodiment of the present invention 1 is provided
The 3rd printing and dyeing mill's sludge EDS analysis results；Figure 14 is the SEM for the 4th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided
Figure, Figure 15 is the EDS analysis results for the 4th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided；Figure 16 is the embodiment of the present invention 1
The SEM figures of the 5th printing and dyeing mill's sludge provided, Figure 17 is EDS points of the 5th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided
Analyse result；Figure 18 is the SEM figures for the 6th printing and dyeing mill's sludge that the embodiment of the present invention 1 is provided, and Figure 19 is that the embodiment of the present invention 1 is carried
The EDS analysis results of the 6th printing and dyeing mill's sludge supplied.By Fig. 8~19 as can be seen that printing and dyeing sludge sample be respectively provided with it is loose many
The flocculation structure in hole, TDP 1,2,3,4 mud sample is presented flower-shaped and bar-shaped, and its main component contains the elements such as Fe, C, O,
And TDP 5,6 mud sample is the uneven graininess of size, its main component is containing elements such as Al, C, O.To sum up, it can push away
The main component of printing and dyeing sludge is surveyed for unbodied flco composition and containing a small amount of AlOOH, CaCO3Crystalline texture.And flocculate into
Divide and probably add the substantial amounts of flocculant containing Al and Fe during treatment of dyeing wastewater, Ca source is and waste water
The CaO added in processing procedure is relevant as pH adjusting agent.Therefore, the present invention will use PFS and PAC, be separately added into milk of lime,
Prepare the inorganic constituents of printing and dyeing sludge simulated system.
Embodiment 2：
The structure of printing and dyeing sludge simulated system
PAC and PFS are configured to 5wt% solution respectively, milk of lime is added dropwise, regulation pH value is obtained to 7.0 or so
Flocculation composition for simulation printing and dyeing sludge inorganic constituents.After centrifugation, the freeze-dried sludge containing PAC respectively obtained it is inorganic into
Divide analogies and the inorganic constituents analogies of sludge containing PFS,
Obtained the inorganic constituents analogies of sludge containing PAC and the inorganic constituents of sludge containing PFS analogies carry out XRF, XRD respectively
Analyzed with SEM-EDS, as a result as shown in Figure 20~26.Figure 20 is the inorganic constituents mould of sludge containing PFS that the embodiment of the present invention 2 is provided
Intend the XRF analysis figure of thing；Figure 21 is the XRF analysis figure for the inorganic constituents analogies of sludge containing PAC that the embodiment of the present invention 2 is provided；
Figure 22 is the XRD spectra for the sludge inorganic constituents analogies that the embodiment of the present invention 2 is provided；Figure 23 is that the embodiment of the present invention 2 is provided
The inorganic constituents analogies of sludge containing PFS SEM figure, Figure 24 be the embodiment of the present invention 2 provide the inorganic constituents mould of sludge containing PFS
Intend the EDS analysis results of thing；Figure 25 is the SEM figures for the inorganic constituents analogies of sludge containing PAC that the embodiment of the present invention 2 is provided；Figure
26 be the EDS analysis results for the inorganic constituents analogies of sludge containing PAC that the embodiment of the present invention 2 is provided.
XRF, which is studied, to be shown, Al in the sludge inorganic constituents analogies containing PAC2O340.15wt% is accounted for, content is than addition Al-
The Al for the printing and dyeing sludge TDP5 and 6 that base flocculant is obtained2O3High 12.06wt% and 5.49wt%.Sludge inorganic constituents containing PFS
Fe in analogies2O326.62wt% is accounted for, Fe in the printing and dyeing sludge obtained with addition Fe- bases flocculant2O3Content it is basically identical,
But CaO accounts for 26.10wt%, the content (10.21~25.37wt%) than CaO in actual printing and dyeing sludge is high, SO3Content be
35.32wt%, it is higher than 1.84~5.11wt% in actual printing and dyeing sludge, it mainly with the addition of the SO that PFS is caused3Increase, simulate
The PAC and PFS of sludge derive from industrial flocculant, and the composition than actual sludge is simple.
XRD results show that the sludge inorganic constituents analogies that PFS, PAC are built are amorphous flocculation structure, with reality
Sludge is almost consistent.SEM-EDS charts are bright, the essential element compositions of the sludge inorganic constituents analogies containing PFS be O, Fe, C,
Ca, S, also containing a small amount of S, Ti, Mg and Si, with the TDP 1-4 in actual interpolation Fe- bases flocculant acquisition printing and dyeing sludge almost
Unanimously.And the sludge inorganic constituents analogies containing PAC mainly contain O, Cl, Al, Ca and Mg, obtained with actual interpolation Al- base flocculants
The TDP 5-6 for obtaining sludge are almost consistent, so as to illustrate, the inorganic constituents using PFS and PAC as printing and dyeing sludge simulated system is
Feasible.
Embodiment 3：
DDM intermediate product research in degraded simulation sludge system
The inorganic constituents analogies of sludge containing PAC and the inorganic constituents mould of sludge containing PFS prepared by 5g embodiment 2 are weighed respectively
Intend thing in 250ml beaker, add the DDM standard liquids that methanol is dissolved in containing 20mg, air-dry after mixing, add in fume hood
200ml water is made into the simulation sludge consistent with actual concentration basin sludge moisture content (about 98wt%), and obtained sludge is print
Stain the simulation composition (including organic principle and inorganic constituents) of mud；
Through ultrasonic in combination potassium permanganate oxidation (US-KMnO4) after reaction, i.e., ultrasonic density is 0.36W/cm3, KMnO4Amount
For 0.12mM, the reaction time is reacts under conditions of 5min after, hydroxylamine hydrochloride quenching Mn (VII) is added, aqueous phase extracts by liquid liquid
Take, mud is after ultrasonic extraction, and nitrogen is blown after concentration, be separately added into double (trimethylsilyl) trifluoroacetamides of 50 μ l N, O-
After 50 μ l pyridine derivatives, detected using GC-MS；
Product analysis is analyzed using 7890-5975 types GC-MS (Agilent companies of the U.S.), and chromatographic column selects HP-5
Type quartz capillary column (30m × 0.25mm × 0.25 μm).Analytical test strip part is：He is as carrier gas, and flow is 1.2ml/
Min, injector temperature sets 280 DEG C, and column temperature is 40 DEG C, and 100 DEG C are risen to by 6 DEG C/min of heating rate after keeping 2min, then
With 10 DEG C/min to 280 DEG C of heating rate；Solvent delay 4min, not shunt mode, sample size is 1.0 μ L；Mass scan range
For 40~300amu；Electron bombardment energy is 70eV；Ion source temperature is 280 DEG C.
DDM catabolite in 1 two kinds of simulation printing and dyeing sludges of table
As shown in Table 1, through US-KMnO4After degraded, the DDM in two kinds of simulation sludge degrade four kinds of intermediate products, respectively
For 3 methoxy 4 hydroxymandelic acid, 3- methoxy-4-phenol methanols, m-methoxybenzoic acid, benzoic acid.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of printing and dyeing sludge inorganic constituents analogies, are prepared in accordance with the following methods：
A), flocculant and calcium compound are mixed in a solvent, obtain the mixed liquor that pH value is 6.5~7.5；
The flocculant includes aluminium polychloride or bodied ferric sulfate；The calcium compound includes calcium hydroxide and/or calcium oxide；
B), the mixed liquor carries out separation of solid and liquid, and isolated solid formation is dried afterwards, printing and dyeing sludge is obtained inorganic
Composition analogies.
2. printing and dyeing sludge inorganic constituents analogies according to claim 1, it is characterised in that the step a) is specifically wrapped
Include：
A1), flocculant and solvent are mixed, flocculant solution is obtained；
A2 calcium compound), is added into the flocculant solution, stops addition after solution ph is 6.5~7.5, is mixed
Close liquid.
3. printing and dyeing sludge inorganic constituents analogies according to claim 2, it is characterised in that the flocculant solution it is dense
Spend for 3~10wt%.
4. printing and dyeing sludge inorganic constituents analogies according to claim 1, it is characterised in that in step b), the drying
Mode be lyophilized.
5. a kind of printing and dyeing sludge analogies, including the print described in printing and dyeing sludge organic principle, water and any one of Claims 1 to 4
Stain mud inorganic constituents analogies.
6. printing and dyeing sludge analogies according to claim 5, it is characterised in that the printing and dyeing sludge organic principle and printing and dyeing
The mass ratio of sludge inorganic constituents analogies is (10~100)：(1000~10000)；
The moisture content of the printing and dyeing sludge analogies is 90~99wt%.
7. printing and dyeing sludge analogies according to claim 5, it is characterised in that the printing and dyeing sludge organic principle includes many
PAH and/or aromatic amine.
The analysis method of situation 8. a kind of organic matter is degraded in printing and dyeing sludge, comprises the following steps：
A the printing and dyeing sludge inorganic constituents analogies mixing described in organic matter, water and any one of Claims 1 to 4), is analysed to,
Obtain printing and dyeing sludge analogies；
B oxidative degradation, printing and dyeing sludge analogies after being degraded), are carried out to the printing and dyeing sludge analogies；
C composition detection), is carried out to printing and dyeing sludge analogies after the degraded, testing result is obtained.
9. analysis method according to claim 8, it is characterised in that step B) in, the mode of the oxidative degradation is：
Oxidant is added in the printing and dyeing sludge analogies.
10. analysis method according to claim 8, it is characterised in that step B) in, the oxidative degradation is deposited in ultrasonic wave
Carried out lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710321150.6A CN106990184B (en) | 2017-05-09 | 2017-05-09 | Inorganic component simulant of printing and dyeing sludge and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710321150.6A CN106990184B (en) | 2017-05-09 | 2017-05-09 | Inorganic component simulant of printing and dyeing sludge and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106990184A true CN106990184A (en) | 2017-07-28 |
| CN106990184B CN106990184B (en) | 2020-10-23 |
Family
ID=59418594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710321150.6A Expired - Fee Related CN106990184B (en) | 2017-05-09 | 2017-05-09 | Inorganic component simulant of printing and dyeing sludge and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106990184B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013006174A (en) * | 2011-05-24 | 2013-01-10 | Hakki Sangyo Kk | Flocculant composition and flocculation method for purifying dye wastewater |
| CN103304054A (en) * | 2013-06-16 | 2013-09-18 | 德州学院 | Printing and dyeing wastewater treatment method |
| CN105948318A (en) * | 2016-06-08 | 2016-09-21 | 浙江奇彩环境科技股份有限公司 | Recycling treatment method for positive ion dye wastewater |
| CN105984929A (en) * | 2016-01-21 | 2016-10-05 | 南京大学 | Aluminum-zinc polysilicate composite flocculating agent and application thereof |
-
2017
- 2017-05-09 CN CN201710321150.6A patent/CN106990184B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013006174A (en) * | 2011-05-24 | 2013-01-10 | Hakki Sangyo Kk | Flocculant composition and flocculation method for purifying dye wastewater |
| CN103304054A (en) * | 2013-06-16 | 2013-09-18 | 德州学院 | Printing and dyeing wastewater treatment method |
| CN105984929A (en) * | 2016-01-21 | 2016-10-05 | 南京大学 | Aluminum-zinc polysilicate composite flocculating agent and application thereof |
| CN105948318A (en) * | 2016-06-08 | 2016-09-21 | 浙江奇彩环境科技股份有限公司 | Recycling treatment method for positive ion dye wastewater |
Non-Patent Citations (5)
| Title |
|---|
| GANG HAN 等: "Combination of forward osmosis (FO) process with coagulation/flocculation (CF) for potential treatment of textile wastewater", 《WATER RESEARCH》 * |
| IMEN KHOUNI 等: "Decolourization of the reconstituted textile effluent by different process treatments:Enzymatic catalysis, coagulation/flocculation and nanofiltration processes", 《DESALINATION》 * |
| JIEYING LIANG 等: "Degradation of aromatic amines in textile-dyeing sludge by combining the ultrasound technique with potassium permanganate treatment", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 涂勇 等: "江苏省印染污泥现状分析", 《环境科学学报》 * |
| 王宝宗 等: "采用内电解法对印染废水进行深度处理", 《环境工程》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106990184B (en) | 2020-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mashkoor et al. | Preparation, characterization and adsorption studies of the chemically modified Luffa aegyptica peel as a potential adsorbent for the removal of malachite green from aqueous solution | |
| Kecić et al. | Optimization of azo printing dye removal with oak leaves-nZVI/H2O2 system using statistically designed experiment | |
| Kalmykova et al. | Sorption and degradation of petroleum hydrocarbons, polycyclic aromatic hydrocarbons, alkylphenols, bisphenol A and phthalates in landfill leachate using sand, activated carbon and peat filters | |
| Diez et al. | Adsorption of phenolic compounds and color from bleached Kraft mill effluent using allophanic compounds | |
| Giannis et al. | Chelating agent-assisted electrokinetic removal of cadmium, lead and copper from contaminated soils | |
| Arienzo | Degradation of 2, 4, 6-trinitrotoluene in water and soil slurry utilizing a calcium peroxide compound | |
| Chen et al. | Molecular-level insights into the transformation mechanism for refractory organics in landfill leachate when using a combined semi-aerobic aged refuse biofilter and chemical oxidation process | |
| Gürses et al. | Removal of dyes and pigments from industrial effluents | |
| Saitoh et al. | Surfactant-coated aluminum hydroxide for the rapid removal and biodegradation of hydrophobic organic pollutants in water | |
| Ghobadi et al. | Copper removal from contaminated soil through electrokinetic process with reactive filter media | |
| Bai et al. | Photon-induced redox chemistry on pyrite promotes photoaging of polystyrene microplastics | |
| Tou et al. | Titanium and zinc-containing nanoparticles in estuarine sediments: Occurrence and their environmental implications | |
| Rodriguez et al. | Phenanthrene degradation in soil by ozonation: Effect of morphological and physicochemical properties | |
| Zhang et al. | Adsorption of sediment phosphorus by porous ceramic filter media coated with nano-titanium dioxide film | |
| CN104858229A (en) | High-efficiency and global-function soil repair agent and preparation method thereof | |
| Taghinia et al. | Heavy metal pollution in Kabini River sediments | |
| Imai et al. | Degradation of marine humic acids by ozone-initiated radical reactions | |
| Liang et al. | Influence mechanisms of textile-dyeing sludge characteristics on degradation of anilines by integrated ultrasound-permanganate treatment | |
| Zhao et al. | Dissociation and removal of complex chromium ions containing in dye wastewaters | |
| Li et al. | Influence of the coexisting contaminants on bisphenol A sorption and desorption in soil | |
| Chen et al. | Molecular-level transformation of refractory organic matter during flocculation-ultraviolet/peroxymonosulfate treatment of MBR-treated landfill leachate | |
| Xu et al. | Modified pineapple peel extract coupled with electrokinetic techniques for remediation of chromium-contaminated soil | |
| Yin et al. | Application of synthesized 2, 5-bis (allyloxy) terephthalohydrazide functionalized covalent organic framework material as a fluorescence probe for selective detection of mercury (II) | |
| Yan et al. | Photochemical degradation in natural attenuation of characteristics of petroleum hydrocarbons (C10-C40) in crude oil polluted soil by simulated long term solar irradiation | |
| Calgaro et al. | Consecutive thermal and wet conditioning treatments of sedimentary stabilized cementitious materials from HPSS® technology: Effects on leaching and microstructure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201023 |