CN103949203A - Preparation method of novel compound wastewater treatment adsorbing agent - Google Patents
Preparation method of novel compound wastewater treatment adsorbing agent Download PDFInfo
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- CN103949203A CN103949203A CN201410179972.1A CN201410179972A CN103949203A CN 103949203 A CN103949203 A CN 103949203A CN 201410179972 A CN201410179972 A CN 201410179972A CN 103949203 A CN103949203 A CN 103949203A
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Abstract
The invention provides a preparation method of a novel compound wastewater treatment adsorbing agent. The preparation method comprises the following steps: step one, preparing attapulgite clay powder which is subjected to surface modification by adopting a dendritic quaternary ammonium salt tetramerization surface active agent; step two, preparing nanometer manganese oxide suspension liquid ; step three, preparing potassium ferrate; and step four, compounding products prepared in the step one to three so as to prepare the compound wastewater treatment adsorbing agent. The stain removal capacity of the compound wastewater treatment adsorbing agent for industrial wastewater is greatly improved by combined application of respective stain removal characteristics of attapulgite clay, nanometer manganese oxide and potassium ferrate through mutual compensation and synergistic effects of the attapulgite clay, the nanometer manganese oxide and the potassium ferrate.
Description
Technical field
The present invention relates to technical field of sewage, relate in particular to a kind of preparation method of novel modified attapulgite clay-nano manganese oxide-potassium ferrate compound sewage processing adsorbent.
background technology
Along with expanding economy, the chemical plant of various places is more and more, the focus that is treated as all circles' concern of trade effluent, and at present, Industrial Wastewater Treatment common technology has charcoal absorption, zeolite exchange etc.Active carbon, because of features such as it are expensive, regeneration is complicated, is difficult to extensive use.Natural attapulgite clay is a kind of silicate clay mineral that occurring in nature extensively exists, there is special octahedral structure and higher cation exchange and physical absorption ability, it has the micro-structural of layer chain, fiber is elongated, duct is many, and surface area is larger, generally presents earthy, bulk, there is stronger water imbibition and lower rainwater dilatancy, there is certain viscosity and plasticity preferably after moistening.Concave-convex clay rod, due to its special geological environment, has a wide range of applications, and is more and more concerned in recent years.
At present, the domestic development and application to Concave-convex clay rod, especially utilizes its excellent improvement in performance modification aspect imperfection.Utilize Concave-convex clay rod to carry out the importance that trade effluent processing is Concave-convex clay rod application, the environmental pollution that sewage discharge causes is more and more worth self-examination, utilize Concave-convex clay rod to carry out sewage disposal and be not only economy and technical problem, environmental issue especially, the reserves of China's Concave-convex clay rod are large, of high grade, utilize Concave-convex clay rod to process trade effluent and concerning our country, there is important and far-reaching meaning.
summary of the invention
Technical problem to be solved by this invention is to provide a kind of Concave-convex clay rod-nano manganese oxide compound sewage of novel surface modification and processes adsorbent, utilize Concave-convex clay rod, nano manganese oxide and potassium ferrate decontamination feature separately, use in conjunction, by mutually making up, synergy, has improved the dirt-removing power to trade effluent greatly.
For solving the problems of the technologies described above, the invention provides a kind of preparation method of novel compound sewage processing adsorbent, be prepared from by Concave-convex clay rod being carried out to modification compound other adsorption components.
The present invention also provides a kind of novel compound sewage to process the preparation method of adsorbent, and it comprises:
The first step, preparation adopts the poly-surfactant of dendroid quaternary ammonium salt four to carry out the Concave-convex clay rod powder of surface modification;
Second step, prepares nano manganese oxide suspension;
The 3rd step, prepares potassium ferrate;
The 4th step, the compound compound sewage inorganic agent of preparing of product prepared by the first step to the three steps.
Wherein, the preparation method of described dendroid quaternary ammonium salt four poly-surfactants is specially: in the 250ml there-necked flask that condenser pipe is housed, add absolute ethyl alcohol 40ml, ethylenediamine 4.5g, room temperature is carried out magnetic agitation, add epoxychloropropane 34.7g with 10/min, dropwise rear back flow reaction 4h.After decompression distillation, obtain four poly-surfactant-intermediates, for faint yellow translucent thick liquid, get this intermediate 20g, the absolute ethyl alcohol taking volume ratio as 1:1 and deionized water mixed solution 40ml are solvent, then drip 7.9gN, N-dimethyl dodecyl tertiary amine, be warming up to 80 DEG C, reaction 1h, decompression distillation, recrystallization, vacuum drying obtains white powder solid and is the poly-surfactant of dendroid quaternary ammonium salt four.
Wherein, the described first step is specially Concave-convex clay rod is joined in deionized water, stir 30min~1h, be warming up to afterwards 30 DEG C~50 DEG C, add the poly-surfactant of dendroid quaternary ammonium salt four of described preparation, stirring reaction 5~10h, filter, washing, dry, pulverizing, the Concave-convex clay rod powder of acquisition modification.
Wherein, described second step is specially at the temperature of 25 DEG C, under hyperacoustic effect, the liquor potassic permanganate that is 0.1ml/L by 40ml concentration is slowly added drop-wise to and is equipped with in the conical flask that 4ml concentration is 1.5mol/L manganese acetate solution, dropwises ultrasonic 5~10 min of rear continuation.The brown color manganese dioxide suspension 8000 r/min high speed centrifugations that reaction is obtained, abandoning supernatant, deionized water is washed till neutrality, adds 43.5mL deionized water to make MnO
2suspension, mass concentration is about 20g/L, and 0~4 DEG C of preservation is for subsequent use.
Wherein, described the 3rd step is specially: take 6.0g Fe(NO3)39H2O (Fe (NO
3)
39H
2o), NaOH 3.0g, in ice bath, in 20ml clorox (NaClO), add sodium hydrate solid, being stirred to solid dissolves completely, continue to add NaOH to saturated, continue to stir 0.5h, then add several times, on a small quantity Fe(NO3)39H2O (Fe (NO
3)
39H
2o), control reaction temperature at 25 DEG C, constantly stir 1.5h, solution gradually becomes royal purple, and showing has Na
2feO
4generate, under agitation, add solid sodium hydroxide again to reach capacity, then continue to stir the thickness that 0.5h solution becomes, centrifugal, suction filtration, obtains Na
2feO
4solution;
Keeping solution temperature is 25 DEG C, add saturated potassium hydroxide solution, stir 15min, there is atropurpureus precipitation to generate, suction filtration, obtains potassium ferrate crude product, and crude product is dissolved with the potassium hydroxide solution of 3mol/L, add saturated potassium hydroxide solution, put into ice bath cooling, have solid to wash out, suction filtration, filter residue removes and anhydrates with cyclohexane, remove lixiviating with absolute ethanol washing again, finally remove second alcohol and water with ether, 60 DEG C of vacuum drying, the vacuum desiccator that is placed in silica gel water absorbing agent is dry, obtains potassium ferrate.
Wherein, the Concave-convex clay rod powder that described the 4th step is specially surface modification prepared by the first step mixes according to the ratio of mass ratio 1:10 with distilled water, be configured to suspension, pour in there-necked flask, the potassium ferrate that adds in proportion again nano manganese oxide suspension prepared by second step and the 3rd step to prepare, speed with 200r/min stirs, 85 DEG C of constant temperature stir after 3 h, product is through suction filtration, washing 3 times, after 110 DEG C of dry 1 h, put into 350 DEG C of calcining 3 h of Muffle furnace, obtain compound sewage inorganic agent.
Beneficial effect of the present invention:
Compound sewage provided by the invention is processed adsorbent Concave-convex clay rod, nano manganese oxide and potassium ferrate is prepared into compound formulation, utilize Concave-convex clay rod, nano manganese oxide and potassium ferrate decontamination feature separately, use in conjunction, by mutually making up, synergy, has improved the dirt-removing power to trade effluent greatly.
brief description of the drawings
Fig. 1 is the XRD figure of the compound sewage inorganic agent prepared of Concave-convex clay rod after Concave-convex clay rod former state, surface modification and the present invention, and in figure, A represents that Concave-convex clay rod former state, B represent that Concave-convex clay rod, C after surface modification represent compound sewage inorganic agent prepared by the present invention;
Fig. 2 is the IR figure of the compound sewage inorganic agent prepared of Concave-convex clay rod after Concave-convex clay rod former state, surface modification and the present invention, and in figure, A represents that Concave-convex clay rod former state, B represent that Concave-convex clay rod, C after surface modification represent compound sewage inorganic agent prepared by the present invention.
Detailed description of the invention
Concave-convex clay rod refers to a kind of clay mineral taking attapulgite (attapulgite) as key component.Attapulgite is a kind of crystalloid hydrous magnesium aluminium silicate mineral, has unique layer chain structure feature, in its structure, has crystal lattice, the Na that contains non-quantitative in side crystal
+, Ca
2+, Fe
3+, Al
3+, crystal is needle-like, fibrous or fiber collection shape.Attapulgite has unique dispersion, high temperature resistant, the anti-good colloidal nature such as saline and alkaline and higher adsorption bleaching ability.And thering is certain plasticity and cohesive force, its desirable chemical molecular formula is: Mg
5si
8o
20(OH)
2(OH
2)
44H2O, has the intermediate structure between chain structure and layer structure.No matter be in adsorption process, or in sewage disposal, Concave-convex clay rod can be regenerated, its power consumption is few, highly beneficial to environmental protection.
Because Concave-convex clay rod is natural, therefore having some limitations property more or less, adopt organic substance to carry out modification and can improve to a great extent these defects of Concave-convex clay rod, the present invention is the impurity in disposing of sewage, adopt organic substance to carry out modification to Concave-convex clay rod, improve it and replace performance and absorption property, Concave-convex clay rod after treatment becomes a kind of organic-inorganic composition, the organic group that molecular weight is very large has replaced the original cation of Concave-convex clay rod, simultaneously, the particle surface meeting adsorb organic compound matter of Concave-convex clay rod, crystal structure is inner can embed organic matter, replace the original crystallization water, the hydrophobicity of Concave-convex clay rod is strengthened greatly, improve the performance of absorption organic pollution, reach the efficiency that improves sewage disposal.
organic surface modifying material provided by the invention is specially the poly-surfactant of dendroid quaternary ammonium salt four, and its structure is specifically suc as formula shown in I:
Formula I
The concrete preparation method of described organic surface modifying material is: in the 250ml there-necked flask that condenser pipe is housed, add absolute ethyl alcohol 40ml, ethylenediamine 4.5g, room temperature is carried out magnetic agitation, add epoxychloropropane 34.7g with 10/min, dropwise rear back flow reaction 4h.After decompression distillation, obtain four poly-surfactant-intermediates, for faint yellow translucent thick liquid, get this intermediate 20g, the absolute ethyl alcohol taking volume ratio as 1:1 and deionized water mixed solution 40ml are solvent, then drip 7.9gN, N-dimethyl dodecyl tertiary amine, be warming up to 80 DEG C, reaction 1h, decompression distillation, recrystallization, vacuum drying obtains white powder solid and is the poly-surfactant of dendroid quaternary ammonium salt four.
Synthetic route is as follows:
The present invention also provides a kind of Concave-convex clay rod that adopts organic surface modifying substance modification, its raw material comprises Concave-convex clay rod and the poly-surfactant of dendroid quaternary ammonium salt four, with respect to the Concave-convex clay rod of 100 weight portions, the addition of the poly-surfactants of dendroid quaternary ammonium salt four is 10 weight portion~20 weight portions, further preferred 15 weight portions.
The present invention also provides the method for modifying of Concave-convex clay rod, is specially:
Concave-convex clay rod is joined in deionized water, stir 30min~1h, be warming up to afterwards 30 DEG C~50 DEG C, add the poly-surfactant of dendroid quaternary ammonium salt four of preparing above, stirring reaction 5~10h, filters, washing, dry, pulverizing, the Concave-convex clay rod powder of acquisition modification.
Manganese oxide is a kind of amphoteric metal oxide, and nanoscale manganese oxide has the features such as specific area is large, ion-exchange capacity is strong, not only to heavy metal ion in water as Pb
2+, Cd
2+, Cu
2+, Ni
2+there is good removal ability, and As (III) and As (V) are had to very strong oxidation and adsorption capacity.
The preparation method of nano manganese oxide is specially:
At the temperature of 25 DEG C, under hyperacoustic effect, the liquor potassic permanganate that is 0.1ml/L by 40ml concentration is slowly added drop-wise to and is equipped with in the conical flask that 4ml concentration is 1.5mol/L manganese acetate solution, dropwises ultrasonic 5~10 min of rear continuation.The brown color manganese dioxide suspension 8000 r/min high speed centrifugations that reaction is obtained, abandoning supernatant, deionized water is washed till neutrality, adds 43.5mL deionized water to make MnO
2suspension, mass concentration is about 20g/L, 0~4 DEG C of preservation, for subsequent use, reaction equation is as follows:
2KMnO
4?+?3Mn?(Ac)
2+?2H
2O→?5MnO
2+?2KAc?+4HAc。
Potassium ferrate can sterilizing, and the reducing substanceses such as ammonia nitrogen in oxidation removal water, sulphur class material, phenols, can not form organic chloride, cause secondary pollution, and security is reliably guaranteed, and meanwhile, decomposition soluble in water produces (Fe (OH)
3) suspension in water is had to an effect of flocculation, absorption and co-precipitation.
The preparation method of potassium ferrate is specially:
The first step, takes 6.0g Fe(NO3)39H2O (Fe (NO
3)
39H
2o), NaOH 3.0g, in ice bath, in 20ml clorox (NaClO), add sodium hydrate solid, being stirred to solid dissolves completely, continue to add NaOH to saturated, continue to stir 0.5h, then add several times, on a small quantity Fe(NO3)39H2O (Fe (NO
3)
39H
2o), control reaction temperature at 25 DEG C, constantly stir 1.5h, solution gradually becomes royal purple, and showing has Na
2feO
4generate, under agitation, add solid sodium hydroxide again to reach capacity, then continue to stir the thickness that 0.5h solution becomes, centrifugal, suction filtration, obtains Na
2feO
4solution;
Second step, keeping solution temperature is 25 DEG C, add saturated potassium hydroxide solution, stir 15min, have atropurpureus precipitation to generate, suction filtration, obtain potassium ferrate crude product, crude product is dissolved with the potassium hydroxide solution of 3mol/L, add saturated potassium hydroxide solution, put into ice bath cooling, there is solid to wash out, suction filtration, filter residue with cyclohexane except anhydrating, then with absolute ethanol washing except lixiviating, finally remove second alcohol and water with ether, 60 DEG C of vacuum drying, the vacuum desiccator that is placed in silica gel water absorbing agent is dry, obtains potassium ferrate.
The present invention utilizes Concave-convex clay rod, nano manganese oxide and potassium ferrate decontamination feature separately by the Concave-convex clay rod by organic surface modifying substance modification, potassium ferrate and nano manganese oxide being prepared into compound formulation, use in conjunction, by mutually making up, synergy, greatly improve the dirt-removing power to trade effluent, in this compound sewage absorbent, main component is Concave-convex clay rod, adopts it as carrier.
The present invention also provides a kind of modified attapulgite clay-nano manganese oxide-potassium ferrate compound sewage to process adsorbent, and its raw materials comprises the above-mentioned Concave-convex clay rod that passes through organic surface modifying substance modification, above-mentioned nano manganese oxide and above-mentioned potassium ferrate.
Further, described compound sewage is processed adsorbent and is prepared from by the above-mentioned Concave-convex clay rod that passes through organic surface modifying substance modification, above-mentioned nano manganese oxide and above-mentioned potassium ferrate.
With respect to the Concave-convex clay rod of the modification of 100 weight portions, the addition of described nano manganese oxide is 8 weight portion~12 weight portions, the addition of described potassium ferrate is 5 weight portion~10 weight portions, further the addition of preferred described nano manganese oxide is 10 weight portions, and the addition of described potassium ferrate is 8 weight portions.
Its preparation method of the present invention is specially:
The first step, adopts the poly-surfactant of dendroid quaternary ammonium salt four to carry out the Concave-convex clay rod powder of surface modification according to method preparation above;
Second step, prepares nano manganese oxide suspension according to method above;
The 3rd step, prepares potassium ferrate according to method above;
The 4th step, the Concave-convex clay rod powder of surface modification prepared by the first step mixes according to the ratio of mass ratio 1:10 with distilled water, be configured to suspension, pour in there-necked flask, then the potassium ferrate that adds in proportion nano manganese oxide suspension prepared by second step and the 3rd step to prepare, speed with 200r/min stirs, 85 DEG C of constant temperature stir after 3 h, and product is through suction filtration, washing 3 times, after 110 DEG C of dry 1 h, put into 350 DEG C of calcining 3 h of Muffle furnace, obtain compound sewage inorganic agent.
Below adopt embodiment to describe embodiments of the present invention in detail, to the present invention, how application technology means solve technical problem whereby, and the implementation procedure of reaching technique effect can fully understand and implement according to this.
The preparation of embodiment 1 dendroid quaternary ammonium salt four poly-surfactants
Be equipped with in the 250ml there-necked flask of condenser pipe, add absolute ethyl alcohol 40ml, ethylenediamine 4.5g, room temperature is carried out magnetic agitation, adds epoxychloropropane 34.7g with 10/min, dropwises rear back flow reaction 4h.After decompression distillation, obtain four poly-surfactant-intermediates, for faint yellow translucent thick liquid, get this intermediate 20g, the absolute ethyl alcohol taking volume ratio as 1:1 and deionized water mixed solution 40ml are solvent, then drip 7.9gN, N-dimethyl dodecyl tertiary amine, be warming up to 80 DEG C, reaction 1h, decompression distillation, recrystallization, vacuum drying obtains white powder solid and is the poly-surfactant of dendroid quaternary ammonium salt four.
The poly-surfactant-modified Concave-convex clay rod of embodiment 2 dendroid quaternary ammonium salt four
100g Concave-convex clay rod is joined in deionized water, stir 1h, be warming up to afterwards 40 DEG C, the poly-surfactant 15g of dendroid quaternary ammonium salt four that adds embodiment 1 to prepare, stirring reaction 7h, filters, washing, dry, pulverizing, the Concave-convex clay rod powder of acquisition modification.
The preparation of embodiment 3 nano-manganese dioxides
At the temperature of 25 DEG C, under hyperacoustic effect, the liquor potassic permanganate that is 0.1ml/L by 40ml concentration is slowly added drop-wise to and is equipped with in the conical flask that 4ml concentration is 1.5mol/L manganese acetate solution, dropwises ultrasonic 5~10 min of rear continuation.The brown color manganese dioxide suspension 8000 r/min high speed centrifugations that reaction is obtained, abandoning supernatant, deionized water is washed till neutrality, adds 43.5mL deionized water to make nano-manganese dioxide suspension, and mass concentration is about 20g/L.
The preparation of embodiment 4 potassium ferrates
Take 6.0g Fe(NO3)39H2O (Fe (NO
3)
39H
2o), NaOH 3.0g, in ice bath, in 20ml clorox (NaClO), add sodium hydrate solid, being stirred to solid dissolves completely, continue to add NaOH to saturated, continue to stir 0.5h, then add several times, on a small quantity Fe(NO3)39H2O (Fe (NO
3)
39H
2o), control reaction temperature at 25 DEG C, constantly stir 1.5h, solution gradually becomes royal purple, and showing has Na
2feO
4generate, under agitation, add solid sodium hydroxide again to reach capacity, then continue to stir the thickness that 0.5h solution becomes, centrifugal, suction filtration, obtains Na
2feO
4solution; Keeping solution temperature is 25 DEG C, add saturated potassium hydroxide solution, stir 15min, there is atropurpureus precipitation to generate, suction filtration, obtains potassium ferrate crude product, and crude product is dissolved with the potassium hydroxide solution of 3mol/L, add saturated potassium hydroxide solution, put into ice bath cooling, have solid to wash out, suction filtration, filter residue removes and anhydrates with cyclohexane, remove lixiviating with absolute ethanol washing again, finally remove second alcohol and water with ether, 60 DEG C of vacuum drying, the vacuum desiccator that is placed in silica gel water absorbing agent is dry, obtains potassium ferrate.
The preparation of embodiment 5 compound sewage inorganic agents 1
The Concave-convex clay rod powder 100g of surface modification prepared by embodiment 2 mixes with 1L distilled water, be configured to suspension, pour in there-necked flask, the potassium ferrate 8g that adds again nano manganese oxide suspension 500ml prepared by embodiment 3 and embodiment 4 to prepare, stirs with the speed of 200r/min, and 85 DEG C of constant temperature stir after 3 h, product is through suction filtration, washing 3 times, after 110 DEG C of dry 1 h, put into 350 DEG C of calcining 3 h of Muffle furnace, obtain compound sewage inorganic agent 1.
Comparative example 1 compound sewage inorganic agent 2
Preparation method is identical with embodiment 5, and difference is that the surface modification of Concave-convex clay rod adopts softex kw to replace the poly-surfactant of dendroid quaternary ammonium salt four, and the method for surface modification is identical with embodiment 2.
Comparative example 2 compound sewage inorganic agents 3
Preparation method is identical with embodiment 5, and difference is that Concave-convex clay rod does not adopt any surface modifier to carry out modification.
Experiment
Experiment material:
Being divided into into 7 groups tests, first group of compound sewage inorganic agent 1 that adopts the embodiment of the present invention 5 to prepare, second group of compound sewage inorganic agent 2 that adopts comparative example 1 to prepare, the 3rd group of compound sewage inorganic agent 3 that adopts comparative example 2 to prepare, potassium ferrate prepared by nano-manganese dioxide prepared by the 4th group of the modified attapulgite clay powder of directly being prepared by embodiment 2, embodiment 3 and embodiment 4 is put into pending sewage in the ratio of embodiment 5, the 5th group of Concave-convex clay rod powder that adopts embodiment 2 to prepare, the addition of respectively organizing inorganic agent is all identical.
Process waste water
Select coal to turn the sewage producing in oily industry.
Processing method
Above-mentioned inorganic agent is added in trade effluent, stir 1h~2h, measure COD, ammonia nitrogen, basicity, BOD, SS and oil index, the indices of waste water carries out monitoring analysis according to " water and waste water detection method " the 4th edition.
Result
Before and after processing, the results are shown in Table 1.
The every result of table 1
The clean effect to industrial wastewater of the compound sewage inorganic agent that as can be seen from Table 1, prepared by the employing embodiment of the present invention 1 is obvious.
All above-mentioned these intellectual properties of primary enforcement, do not set restriction this new product of other forms of enforcement and/or new method.Those skilled in the art will utilize this important information, and foregoing amendment, to realize similar implementation status.But all modifications or transformation belong to the right of reservation based on new product of the present invention.
The above, be only preferred embodiment of the present invention, is not the restriction of the present invention being made to other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (7)
1. novel compound sewage is processed a preparation method for adsorbent, it is characterized in that: be prepared from by Concave-convex clay rod being carried out to modification compound other adsorption components.
2. novel compound sewage is processed a preparation method for adsorbent, it is characterized in that, comprising:
The first step, preparation adopts the poly-surfactant of dendroid quaternary ammonium salt four to carry out the Concave-convex clay rod powder of surface modification;
Second step, prepares nano manganese oxide suspension;
The 3rd step, prepares potassium ferrate;
The 4th step, the compound compound sewage inorganic agent of preparing of product prepared by the first step to the three steps.
3. compound sewage as claimed in claim 2 is processed the preparation method of adsorbent, it is characterized in that: the preparation method of described dendroid quaternary ammonium salt four poly-surfactants is specially: in the 250ml there-necked flask that condenser pipe is housed, add absolute ethyl alcohol 40ml, ethylenediamine 4.5g, room temperature is carried out magnetic agitation, add epoxychloropropane 34.7g with 10/min, dropwise rear back flow reaction 4h, after decompression distillation, obtain four poly-surfactant-intermediates, for faint yellow translucent thick liquid, get this intermediate 20g, absolute ethyl alcohol taking volume ratio as 1:1 and deionized water mixed solution 40ml are solvent, drip again 7.9gN, N-dimethyl dodecyl tertiary amine, be warming up to 80 DEG C, reaction 1h, decompression distillation, recrystallization, vacuum drying obtains white powder solid and is the poly-surfactant of dendroid quaternary ammonium salt four.
4. compound sewage is processed the preparation method of adsorbent as claimed in claim 2 or claim 3, it is characterized in that: the described first step is specially Concave-convex clay rod is joined in deionized water, stir 30min~1h, be warming up to afterwards 30 DEG C~50 DEG C, add the poly-surfactant of dendroid quaternary ammonium salt four of described preparation, stirring reaction 5~10h, filter, washing, dry, pulverizing, the Concave-convex clay rod powder of acquisition modification.
5. the compound sewage as described in claim 2 to 4 is processed the preparation method of adsorbent, it is characterized in that: described second step is specially at the temperature of 25 DEG C, under hyperacoustic effect, the liquor potassic permanganate that is 0.1ml/L by 40ml concentration is slowly added drop-wise to and is equipped with in the conical flask that 4ml concentration is 1.5mol/L manganese acetate solution, dropwise ultrasonic 5~10 min of rear continuation, the brown color manganese dioxide suspension 8000 r/min high speed centrifugations that reaction is obtained, abandoning supernatant, deionized water is washed till neutrality, adds 43.5mL deionized water to make MnO
2suspension, mass concentration is about 20g/L, and 0~4 DEG C of preservation is for subsequent use.
6. the compound sewage as described in claim 2 to 5 is processed the preparation method of adsorbent, it is characterized in that: described the 3rd step is specially, and takes 6.0g Fe(NO3)39H2O (Fe (NO
3)
39H
2o), NaOH 3.0g, in ice bath, in 20ml clorox (NaClO), add sodium hydrate solid, being stirred to solid dissolves completely, continue to add NaOH to saturated, continue to stir 0.5h, then add several times, on a small quantity Fe(NO3)39H2O (Fe (NO
3)
39H
2o), control reaction temperature at 25 DEG C, constantly stir 1.5h, solution gradually becomes royal purple, and showing has Na
2feO
4generate, under agitation, add solid sodium hydroxide again to reach capacity, then continue to stir the thickness that 0.5h solution becomes, centrifugal, suction filtration, obtains Na
2feO
4solution;
Keeping solution temperature is 25 DEG C, add saturated potassium hydroxide solution, stir 15min, there is atropurpureus precipitation to generate, suction filtration, obtains potassium ferrate crude product, and crude product is dissolved with the potassium hydroxide solution of 3mol/L, add saturated potassium hydroxide solution, put into ice bath cooling, have solid to wash out, suction filtration, filter residue removes and anhydrates with cyclohexane, remove lixiviating with absolute ethanol washing again, finally remove second alcohol and water with ether, 60 DEG C of vacuum drying, the vacuum desiccator that is placed in silica gel water absorbing agent is dry, obtains potassium ferrate.
7. the compound sewage as described in claim 2 to 6 is processed the preparation method of adsorbent, it is characterized in that: the Concave-convex clay rod powder that described the 4th step is specially surface modification prepared by the first step mixes according to the ratio of mass ratio 1:10 with distilled water, be configured to suspension, pour in there-necked flask, the potassium ferrate that adds in proportion again nano manganese oxide suspension prepared by second step and the 3rd step to prepare, speed with 200r/min stirs, 85 DEG C of constant temperature stir after 3 h, product is through suction filtration, wash 3 times, after 110 DEG C of dry 1 h, put into 350 DEG C of calcining 3 h of Muffle furnace, obtain compound sewage inorganic agent.
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