CN107954492A - Sewage-treating agent of various heavy and preparation method thereof in water can be removed - Google Patents

Sewage-treating agent of various heavy and preparation method thereof in water can be removed Download PDF

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Publication number
CN107954492A
CN107954492A CN201711298636.9A CN201711298636A CN107954492A CN 107954492 A CN107954492 A CN 107954492A CN 201711298636 A CN201711298636 A CN 201711298636A CN 107954492 A CN107954492 A CN 107954492A
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parts
clay
sewage
powder
water
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郭敏
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Hepu County Water Conservancy Bureau
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Hepu County Water Conservancy Bureau
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • C02F2101/18Cyanides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/203Iron or iron compound
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/08Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/14NH3-N
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/18PO4-P

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The present invention provides a kind of sewage-treating agent for removing various heavy in water, including following components:Sepiolite powder, modified clay, polyacrylamide, bentonite, cross-linked rectorite, chitosan, shell, peanut shell, macadamia shell;The preparation method of modified clay is:S1, by clay by room temperature to 500~550 DEG C, and keep 2~3h;750~800 DEG C are then heated to, and keeps 10~15h, is cooled down, is washed, it is dry;S2, by clay add hydrochloric acid in, filtering, add in sodium carbonate, filter, wash, calcination;S3, again add clay in ethanol solution, and stirring, then adds cetyl trimethylammonium bromide, double three quaternary ammonium salts of alkyl polyoxyethylene base, stirs, and filters, and washing, is drying to obtain modified clay.The sewage-treating agent of the present invention is by the way that to the clay modified micropore for making the hole density of increase clay and forming prosperity, specific surface area is big, can remove various metals.

Description

Sewage-treating agent of various heavy and preparation method thereof in water can be removed
Technical field
The present invention relates to water-treatment technology field, and in particular to a kind of sewage-treating agent for removing various heavy in water And preparation method thereof.
Background technology
Heavy metal wastewater thereby is to an environmental pollution most serious and to one of maximum industrial wastewater of mankind's harm, its water quality water Amount is related with production technology.Heavy metal in waste water cannot generally decompose destruction, can only shift its existence position and change its thing Change form.The administering method of heavy metal pollution at present is especially effectively directed to heavy metal-containing waste water based on physico-chemical process The sewage-treating agent of processing is still immature, how to seek at a kind of efficient sewage of low cost for heavy metal-containing wastewater treatment Agent is managed, is a problem for being worth research.
The content of the invention
It is an object of the invention to solve at least the above, and provide the advantages of at least will be described later.
It is an object of the present invention to provide a kind of sewage-treating agent for removing various heavy in water, by clay Speed change heating treatment can make the hole density of increase clay after persalt, sodium carbonate processing again and can form the micropore of prosperity, than Surface area is big, can remove various metals.
In order to realize object of the present invention and further advantage, there is provided a kind of dirt for removing various heavy in water Water treatment agent, including following parts by weight of component:
5~10 parts of sepiolite powder, 25~35 parts of modified clay, 6~7 parts of polyacrylamide, 15~20 parts of bentonite, crosslinking 20~25 parts of rectorite, 3~6 parts of chitosan, 5~10 parts of shell, 1~2 part of peanut shell, 2~3 parts of chestnut shell, walnut shell 1~2 Part, 1~2 part of macadamia shell;
The preparation method of the modified clay comprises the following steps:
S1, by clay with 10~15 DEG C/min by room temperature to 500~550 DEG C, and keep 2~3h;Then with 5~8 DEG C/min is warming up to 750~800 DEG C, and keeps 10~15h, is cooled to room temperature, washs to neutrality, and it is dry, cross 200 mesh sieves;
S2, by cross 200 mesh sieves after clay add mass fraction be 5~10% hydrochloric acid solution in temperature be 60~70 8~12h is stirred at DEG C, is filtered, is washed, it is dry;It is molten that dried clay is added into the sodium carbonate that mass fraction is 15~20% 3~4h is stirred at temperature is 30~35 DEG C in liquid, is filtered, is washed, it is dry, then with the heating rate liter of 15~20 DEG C/min Temperature is to 500~550 DEG C and keeps 3~4h, is cooled to room temperature;
S3, by clay after cooling add mass fraction be 60~70% ethanol solution in, stirring, be heated to 80~90 DEG C, cetyl trimethylammonium bromide, double three quaternary ammonium salts of alkyl polyoxyethylene base are then added, stirring 5~10h of reaction, is filtered, Washing, is drying to obtain modified clay.
Preferably, the sewage-treating agent for removing various heavy in water, clay, cetyl front three in S3 Base ammonium bromide, the mass ratio of double three quaternary ammonium salts of alkyl polyoxyethylene base are 1:0.2~0.3:0.1~0.3;Stirring was reacted in S3 It is placed in journey every 2~3h in the micro-wave oven that power is 250~300W and reacts 3~5min.
A kind of preparation method for removing the sewage-treating agent of various heavy in water, comprises the following steps:
Step 1: it is the sodium carbonate liquor that mass concentration is 5~10% that the shell that parts by weight are 5~10 parts is placed in concentration 5~10h of middle immersion, takes out, and cleaning, drying obtain the first powder after crushing;
Step 2: by parts by weight be 1~2 part peanut shell, 2~3 parts of chestnut shell, 1~2 part of walnut shell, 1~2 part Macadamia shell, the first powder, 15~20 parts of bentonite co-grinding after temperature be 500~550 DEG C at calcination 0.5~ 1h, is then warming up to 700~750 DEG C with 10~15 DEG C/min and keeps 10~20min, then is cooled to 400 with 6~8 DEG C/min ~450 DEG C and 20~30min of holding, then 1000~1100 DEG C are warming up to 12~15 DEG C/min and keep 2~3h, it is last cold But to room temperature, the second powder is obtained;
Step 3: by the second powder mull crush, add mass fraction be 5~10% acetum in immersion 5~ 10min, filtering, cleaning, drying, will dried second powder add metal salt solution in temperature be 400~500 DEG C at instead 15~20h is answered, is cooled down, filtering, dry the 3rd powder;The metal salt solution is to include ferric sulfate, ferrous sulfate, sulfuric acid The aqueous solution of copper, nickel sulfate;
Step 4: the sepiolite powder, 25~35 parts of modified clay, 20~25 parts of crosslinking that are 5~10 parts by parts by weight Rectorite, 400~450 parts of water, the 3rd powder are uniformly mixed and are made into suspension;The chitosan that parts by weight are 3~6 parts is dissolved in The chitosan solution that mass concentration is 3~5% is configured in water, chitosan solution is added in the suspension in step 4, in Temperature is that 3~4h is stirred at 60~70 DEG C, is cooled down, and filtering, drying obtains the 5th powder;
Step 5: polyacrylamide that parts by weight are 6~7 parts, the 5th powder obtained in step 4 are added into parts by weight For in 350~400 parts of water in temperature be at 60~65 DEG C stirring 3~4h, cool down, filtering, be drying to obtain sewage-treating agent.
Preferably, the preparation method for removing the sewage-treating agent of various heavy in water, in step 3 Two powder add in metal salt solution and are placed in reacting under nitrogen or argon gas protection environment.
Preferably, the preparation method for removing the sewage-treating agent of various heavy in water, gold in step 3 It is 1 to belong to iron ion in salting liquid, ferrous ion, copper ion, the molar ratio of nickel ion:0.2~0.3:0.5~1:0.4~0.8.
Preferably, the preparation method for removing the sewage-treating agent of various heavy in water, is stirred in step 5 It is 400~600r/min to mix speed.
The present invention includes at least following beneficial effect:
1st, the sewage-treating agent for removing various heavy in water of the invention, by being passed through again to the heating treatment of clay speed change It can make the hole density of increase clay after persalt, sodium carbonate processing and the micropore of prosperity can be formed, specific surface area is big, adsorbable Various metals;Then further clay is changed by cetyl trimethylammonium bromide, double three quaternary ammonium salts of alkyl polyoxyethylene base Property, since cetyl trimethylammonium bromide, three quaternary ammonium salt organic quaternary ammonium salt of double alkyl polyoxyethylene bases are organic cation, its Clay surface, which can be covered in, makes clay surface be changed into lipophile from hydrophily, makes it can be with the oily substance in absorption effluent; Sepiolite powder has specific surface area maximum in nonmetallic mineral and unique pore passage structure, adsorption capacity in sewage-treating agent By force;Cross-linked rectorite is strong with larger specific surface area, ion exchange capacity and micropore size adsorption capacity;Linear point of chitosan Contain multiple hydroxyls and amino in subchain, can be chelated with metal ions in sewage into stable inner complex salt, be allowed to can remove in water A variety of harmful metal ions, another aspect one side amino can be with H in water+Protonationization forms cationic polyelectrolyte, leads to Cross electrostatic attraction and absorption the thickness particle coacervation in water settles down into big flocculating body, so as to remove COD and SS in water removal.
2nd, the sewage-treating agent for removing various heavy in water of the invention, after shell is crushed with peanut shell, Chinese chestnut Shell, walnut shell, macadamia shell, bentonite mixing segmentation alternating temperature calcination, in calcination peanut shell, chestnut shell, walnut shell, Macadamia shell these vegetalitas shells can a part of Viability charcoal of part cracking gas metaplasia, another part cracking gasification oxidation after-flame Leave hole or passage bentonite, shell can so formed porous, the removal rate of organic and inorganic thing in adsorption filtration sewage It is high;Again by the mixture after calcination, it is dissolved in metal salt solution, mixture area load iron, copper, nickel metal ion can be made, this A little metal ions have catalytic activity, can be catalyzed some organic matters and decompose, and catalysis significantly improves sewage with absorbing synergic effect The removal efficiency of inorganic agent.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this The research and practice of invention and be understood by the person skilled in the art.
Embodiment
With reference to embodiment, the present invention is described in further detail, to make those skilled in the art with reference to specification Word can be implemented according to this.
It should be noted that experimental method described in following embodiments, is conventional method unless otherwise specified, institute Reagent and material are stated, unless otherwise specified, is commercially obtained.
Embodiment 1
A kind of sewage-treating agent for removing various heavy in water, including following parts by weight of component:
5 parts of sepiolite powder, 25 parts of modified clay, 6 parts of polyacrylamide, 15 parts of bentonite, 20 parts of cross-linked rectorite, shell gather 3 parts of sugar, 5 parts of shell, 1 part of peanut shell, 2 parts of chestnut shell, 1 part of walnut shell, 1 part of macadamia shell;
The preparation method of the modified clay comprises the following steps:
S1, by clay with 10 DEG C/min by room temperature to 500 DEG C, and keep 2h;Then being warming up to 5 DEG C/min 750 DEG C, and 10h is kept, it is cooled to room temperature, washs to neutrality, it is dry, cross 200 mesh sieves;
S2, will to cross the clay after 200 mesh sieves and add in the hydrochloric acid solution that mass fraction is 5% in temperature be to be stirred at 60 DEG C 8h, is filtered, and is washed, dry;By dried clay addition mass fraction be 15% sodium carbonate liquor in temperature be 30 DEG C Lower stirring 3h, is filtered, and is washed, dry, is then warming up to 500 DEG C with the heating rate of 15 DEG C/min and is kept 3h, is cooled to room Temperature;
S3, by clay after cooling add mass fraction be 60% ethanol solution in, stirring, be heated to 80 DEG C, then Cetyl trimethylammonium bromide, double three quaternary ammonium salts of alkyl polyoxyethylene base are added, stirring reaction 5h, is filtered, washing, drying is Obtain modified clay.
The sewage-treating agent for removing various heavy in water, clay in S3, cetyl trimethylammonium bromide, The mass ratio of double three quaternary ammonium salts of alkyl polyoxyethylene base is 1:0.2:0.1;Stirred in S3 in reaction process and be placed in power every 2h To react 3min in the micro-wave oven of 250W.
The preparation method for removing the sewage-treating agent of various heavy in water, comprises the following steps:
Step 1: it is to be soaked in the sodium carbonate liquor that mass concentration is 5% that the shell that parts by weight are 5 parts is placed in concentration 5h, takes out, and cleaning, drying obtain the first powder after crushing;
Step 2: by parts by weight be 1 part peanut shell, 2 parts of chestnut shell, 1 part of walnut shell, 1 part of macadamia shell, First powder, 15 parts of bentonite co-grinding are to be calcined 0.5h at 500 DEG C after temperature, are then warming up to 10 DEG C/min 700 DEG C and 10min is kept, then be cooled to 400 DEG C with 6 DEG C/min and keep 20min, be then warming up to 1000 DEG C with 12 DEG C/min And 2h is kept, room temperature is finally cooled to, obtains the second powder;
Step 3: the second powder mull is crushed, add in the acetum that mass fraction is 5% and soak 5min, filter, Cleaning, drying, will react 15h at temperature is 400 DEG C in dried second powder addition metal salt solution, cool down, filtering, Dry the 3rd powder;The metal salt solution is the aqueous solution for including ferric sulfate, ferrous sulfate, copper sulphate, nickel sulfate;
Step 4: by parts by weight be 5 parts sepiolite powder, 25 parts of modified clay, 20 parts of cross-linked rectorite, 400 parts Water, the 3rd powder is uniformly mixed and is made into suspension;It is configured to chitosan that parts by weight are 3 parts is soluble in water mass concentration and is 3% chitosan solution, chitosan solution is added in the suspension in step 4, is to stir 3h at 60 DEG C in temperature, is cooled down, Filtering, drying obtain the 5th powder;
Step 5: the 5th powder obtained in polyacrylamide that parts by weight are 6 parts, step 4 added parts by weight being 3h is stirred at temperature is 60 DEG C in 350 parts of water, is cooled down, filtering, is drying to obtain sewage-treating agent.
The preparation method for removing the sewage-treating agent of various heavy in water, the second powder adds in step 3 It is placed in reacting under nitrogen environmental protection in metal salt solution.
The preparation method for removing the sewage-treating agent of various heavy in water, in step 3 in metal salt solution Iron ion, ferrous ion, copper ion, the molar ratio of nickel ion are 1:0.2:0.5:0.4.
The preparation method for removing the sewage-treating agent of various heavy in water, stirring speed is in step 5 500r/min。
Embodiment 2
A kind of sewage-treating agent for removing various heavy in water, including following parts by weight of component:
8 parts of sepiolite powder, 30 parts of modified clay, 7 parts of polyacrylamide, 18 parts of bentonite, 23 parts of cross-linked rectorite, shell 5 parts of glycan, 8 parts of shell, 2 parts of peanut shell, 3 parts of chestnut shell, 2 parts of walnut shell, 2 parts of macadamia shell;
The preparation method of the modified clay comprises the following steps:
S1, by clay with 12 DEG C/min by room temperature to 530 DEG C, and keep 2h;Then being warming up to 6 DEG C/min 780 DEG C, and 13h is kept, it is cooled to room temperature, washs to neutrality, it is dry, cross 200 mesh sieves;
S2, will to cross the clay after 200 mesh sieves and add in the hydrochloric acid solution that mass fraction is 8% in temperature be to be stirred at 65 DEG C 10h, is filtered, and is washed, dry;By dried clay addition mass fraction be 18% sodium carbonate liquor in temperature be 33 DEG C Lower stirring 4h, is filtered, and is washed, dry, is then warming up to 530 DEG C with the heating rate of 18 DEG C/min and is kept 4h, is cooled to room Temperature;
S3, by clay after cooling add mass fraction be 65% ethanol solution in, stirring, be heated to 85 DEG C, then Cetyl trimethylammonium bromide, double three quaternary ammonium salts of alkyl polyoxyethylene base are added, stirring reaction 8h, is filtered, washing, drying is Obtain modified clay.
The sewage-treating agent for removing various heavy in water, clay in S3, cetyl trimethylammonium bromide, The mass ratio of double three quaternary ammonium salts of alkyl polyoxyethylene base is 1:0.3:0.2;Stirred in S3 in reaction process and be placed in power every 3h To react 3~5min in the micro-wave oven of 280W.
The preparation method for removing the sewage-treating agent of various heavy in water, comprises the following steps:
Step 1: it is to be soaked in the sodium carbonate liquor that mass concentration is 8% that the shell that parts by weight are 8 parts is placed in concentration 8h, takes out, and cleaning, drying obtain the first powder after crushing;
Step 2: by parts by weight be 2 parts peanut shell, 3 parts of chestnut shell, 2 parts of walnut shell, 2 parts of macadamia shell, First powder, 18 parts of bentonite co-grinding are to be calcined 0.8h at 530 DEG C after temperature, are then warming up to 13 DEG C/min 730 DEG C and 15min is kept, then be cooled to 430 DEG C with 7 DEG C/min and keep 25min, be then warming up to 1050 DEG C with 13 DEG C/min And 3h is kept, room temperature is finally cooled to, obtains the second powder;
Step 3: the second powder mull is crushed, add in the acetum that mass fraction is 8% and soak 8min, filter, Cleaning, drying, dried second powder is added in metal salt solution and reacts 18h in temperature for 450 DEG C, is cooled down, and is filtered, and is done It is dry to obtain the 3rd powder;The metal salt solution is the aqueous solution for including ferric sulfate, ferrous sulfate, copper sulphate, nickel sulfate;
Step 4: by parts by weight be 8 parts sepiolite powder, 30 parts of modified clay, 23 parts of cross-linked rectorite, 430 parts Water, the 3rd powder is uniformly mixed and is made into suspension;It is configured to chitosan that parts by weight are 5 parts is soluble in water mass concentration and is 4% chitosan solution, chitosan solution is added in the suspension in step 4, is to stir 4h at 65 DEG C in temperature, is cooled down, Filtering, drying obtain the 5th powder;
Step 5: the 5th powder obtained in polyacrylamide that parts by weight are 7 parts, step 4 added parts by weight being 4h is stirred at temperature is 63 DEG C in 380 parts of water, is cooled down, filtering, is drying to obtain sewage-treating agent.
The preparation method for removing the sewage-treating agent of various heavy in water, the second powder adds in step 3 It is placed in reacting under argon gas protection environment in metal salt solution.
The preparation method for removing the sewage-treating agent of various heavy in water, in step 3 in metal salt solution Iron ion, ferrous ion, copper ion, the molar ratio of nickel ion are 1:0.3:0.8:0.6.
The preparation method for removing the sewage-treating agent of various heavy in water, stir speed (S.S.) is in step 5 500r/min。
Embodiment 3
A kind of sewage-treating agent for removing various heavy in water, including following parts by weight of component:
10 parts of sepiolite powder, 35 parts of modified clay, 7 parts of polyacrylamide, 20 parts of bentonite, 25 parts of cross-linked rectorite, shell 6 parts of glycan, 10 parts of shell, 2 parts of peanut shell, 3 parts of chestnut shell, 2 parts of walnut shell, 2 parts of macadamia shell;
The preparation method of the modified clay comprises the following steps:
S1, by clay with 15 DEG C/min by room temperature to 550 DEG C, and keep 3h;Then being warming up to 8 DEG C/min 800 DEG C, and 15h is kept, it is cooled to room temperature, washs to neutrality, it is dry, cross 200 mesh sieves;
S2, will to cross the clay after 200 mesh sieves and add in the hydrochloric acid solution that mass fraction is 10% in temperature be to be stirred at 70 DEG C 12h is mixed, is filtered, is washed, it is dry;By dried clay addition mass fraction be 20% sodium carbonate liquor in temperature be 35 4h is stirred at DEG C, is filtered, is washed, it is dry, then 550 DEG C are warming up to the heating rate of 20 DEG C/min and keep 4h, be cooled to Room temperature;
S3, by clay after cooling add mass fraction be 70% ethanol solution in, stirring, be heated to 90 DEG C, then Cetyl trimethylammonium bromide, double three quaternary ammonium salts of alkyl polyoxyethylene base are added, stirring reaction 10h, filters, wash, dry Up to modified clay.
The sewage-treating agent for removing various heavy in water, clay in S3, cetyl trimethylammonium bromide, The mass ratio of double three quaternary ammonium salts of alkyl polyoxyethylene base is 1:0.3:0.3;Stirred in S3 in reaction process and be placed in power every 3h To react 5min in the micro-wave oven of 300W.
The preparation method for removing the sewage-treating agent of various heavy in water, comprises the following steps:
Step 1: it is to be soaked in the sodium carbonate liquor that mass concentration is 10% that the shell that parts by weight are 10 parts is placed in concentration 10h, takes out, and cleaning, drying obtain the first powder after crushing;
Step 2: by parts by weight be 2 parts peanut shell, 3 parts of chestnut shell, 2 parts of walnut shell, 2 parts of macadamia shell, First powder, 20 parts of bentonite co-grinding are to be calcined 1h at 550 DEG C after temperature, are then warming up to 750 with 15 DEG C/min DEG C and keep 20min, then be cooled to 450 DEG C with 8 DEG C/min and keep 30min, be then warming up to 1100 DEG C simultaneously with 15 DEG C/min 3h is kept, room temperature is finally cooled to, obtains the second powder;
Step 3: the second powder mull is crushed, add in the acetum that mass fraction is 10% and soak 10min, mistake Filter, cleaning, drying, dried second powder is added in metal salt solution and reacts 20h, cooling, mistake in temperature for 500 DEG C Filter, dry the 3rd powder;The metal salt solution is the aqueous solution for including ferric sulfate, ferrous sulfate, copper sulphate, nickel sulfate;
Step 4: by parts by weight be 10 parts sepiolite powder, 35 parts of modified clay, 25 parts of cross-linked rectorite, 450 parts Water, the 3rd powder is uniformly mixed and is made into suspension;It is configured to chitosan that parts by weight are 6 parts is soluble in water mass concentration and is 5% chitosan solution, chitosan solution is added in the suspension in step 4, is to stir 4h at 70 DEG C in temperature, is cooled down, Filtering, drying obtain the 5th powder;
Step 5: the 5th powder obtained in polyacrylamide that parts by weight are 7 parts, step 4 added parts by weight being 4h is stirred at temperature is 65 DEG C in 400 parts of water, is cooled down, filtering, is drying to obtain sewage-treating agent.
The preparation method for removing the sewage-treating agent of various heavy in water, the second powder adds in step 3 It is placed in reacting under nitrogen environmental protection in metal salt solution.
The preparation method for removing the sewage-treating agent of various heavy in water, in step 3 in metal salt solution Iron ion, ferrous ion, copper ion, the molar ratio of nickel ion are 1:0.3:1:0.8.
The preparation method for removing the sewage-treating agent of various heavy in water, stir speed (S.S.) is in step 5 600r/min。
Comparative example 1
With embodiment 1, difference is, modified clay is not contained in sewage-treating agent.
Comparative example 2
With embodiment 1, difference is, the second powder is added without in metal salt solution in sewage-treating agent step 3 is prepared Reaction.
Carrying out lab scale processing to certain grease containing heavy metal, the wherein COD in grease is 832mg/L, SS 186mg/L, Cu2+For 86mg/L, Cd2+For 76mg/L, Ni2+For 23mg/L, Cr3+For 13mg/L, oil content 298mg/L;Using embodiment 1~ 3rd, sewage-treating agent prepared by comparative example 1 handles grease respectively, and the results are shown in Table 1 for the water quality index after detection process, in table Each index unit is mg/L.
The influence that table 1- differences embodiment handles grease
Embodiment COD SS Oil content Cu2+ Cd2+ Ni2+ Cr3+
Embodiment 1 48 19 4.6 0.21 1.1 0.18 0.05
Embodiment 2 43 17 4.2 0.19 0.9 0.17 0.04
Embodiment 3 41 15 3.8 0.18 0.8 0.16 0.03
Comparative example 1 59 26 6.3 0.29 1.9 0.26 1.1
From table 1 it follows that various gold after the treating sewage by sewage treating agent of preparation by inventive embodiments 1~3 The index for belonging to ion is less than comparative example 1, illustrates the sewage-treating agent of the present invention and can remove various metals ion in water.
Lab scale is carried out to certain sewage for containing organic matter, total phosphorus is 2.86mg/L wherein in sewage, ammonia nitrogen 21mg/L, cyanogen Compound 3.2mg/L;The sewage-treating agent being prepared using embodiment 1, comparative example 2 is respectively handled sewage, at detection The results are shown in Table 2 for water quality index after reason, and each index unit is mg/L in table.
Influence of the table 2- differences embodiment to sewage disposal
Embodiment Total phosphorus Cyanide Ammonia nitrogen
Embodiment 1 0.32 0.38 11
Comparative example 1 0.45 0.53 15
It is from Table 2, it can be seen that a variety of after the treating sewage by sewage treating agent of preparation by inventive embodiments 1 Organic components are respectively less than comparative example 1, illustrate the second powder being dissolved in metal salt solution, can add after making its loaded metal ion The decomposition of fast organic matter, improves removal rate.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art Realize other modification, therefore under the universal limited without departing substantially from claim and equivalency range, it is of the invention and unlimited In specific details.

Claims (6)

1. a kind of sewage-treating agent for removing various heavy in water, it is characterised in that including following parts by weight of component:
5~10 parts of sepiolite powder, 25~35 parts of modified clay, 6~7 parts of polyacrylamide, 15~20 parts of bentonite, the tired support of crosslinking 20~25 parts of stone, 3~6 parts of chitosan, 5~10 parts of shell, 1~2 part of peanut shell, 2~3 parts of chestnut shell, 1~2 part of walnut shell, Australia 1~2 part of continent shuck;
The preparation method of the modified clay comprises the following steps:
S1, by clay with 10~15 DEG C/min by room temperature to 500~550 DEG C, and keep 2~3h;Then with 5~8 DEG C/ Min's is warming up to 750~800 DEG C, and keeps 10~15h, is cooled to room temperature, and washs to neutrality, dry, crosses 200 mesh sieves;
S2, by cross 200 mesh sieves after clay add mass fraction be 5~10% hydrochloric acid solution in temperature be at 60~70 DEG C 8~12h is stirred, is filtered, is washed, it is dry;Dried clay is added in the sodium carbonate liquor that mass fraction is 15~20% It is that 3~4h is stirred at 30~35 DEG C in temperature, filters, washs, it is dry, then it is warming up to the heating rate of 15~20 DEG C/min 500~550 DEG C and 3~4h of holding, it is cooled to room temperature;
S3, by clay after cooling add mass fraction be 60~70% ethanol solution in, stirring, be heated to 80~90 DEG C, Then cetyl trimethylammonium bromide, double three quaternary ammonium salts of alkyl polyoxyethylene base are added, stirring 5~10h of reaction, filtering, is washed Wash, be drying to obtain modified clay.
2. the sewage-treating agent of various heavy in water can be removed as claimed in claim 1, it is characterised in that clay in S3, Cetyl trimethylammonium bromide, the mass ratio of double three quaternary ammonium salts of alkyl polyoxyethylene base are 1:0.2~0.3:0.1~0.3;S3 It is placed in middle stirring reaction process every 2~3h in the micro-wave oven that power is 250~300W and reacts 3~5min.
3. a kind of preparation method that can remove the sewage-treating agent of various heavy in water as claimed in claim 1, its feature It is, comprises the following steps:
Step 1: it is to be soaked in the sodium carbonate liquor that mass concentration is 5~10% that the shell that parts by weight are 5~10 parts is placed in concentration 5~10h is steeped, is taken out, cleaning, drying obtain the first powder after crushing;
Step 2: it is 1~2 part of peanut shell, 2~3 parts of chestnut shell, 1~2 part of walnut shell, 1~2 part of Australia by parts by weight Continent shuck, the first powder, 15~20 parts of bentonite co-grinding are that 0.5~1h is calcined at 500~550 DEG C after temperature, Then 700~750 DEG C are warming up to 10~15 DEG C/min and keep 10~20min, then 400 are cooled to 6~8 DEG C/min~ 450 DEG C and 20~30min of holding, then 1000~1100 DEG C are warming up to 12~15 DEG C/min and keep 2~3h, finally cooled down To room temperature, the second powder is obtained;
Step 3: the second powder mull is crushed, add in the acetum that mass fraction is 5~10% and soak 5~10min, Filtering, cleaning, drying, will dried second powder add metal salt solution in temperature be 400~500 DEG C at react 15~ 20h, cools down, filtering, dry the 3rd powder;The metal salt solution is to include ferric sulfate, ferrous sulfate, copper sulphate, sulfuric acid The aqueous solution of nickel;
Step 4: the sepiolite powder, 25~35 parts of modified clay, 20~25 parts of crosslinking that parts by weight are 5~10 parts are tired out into support Stone, 400~450 parts of water, the 3rd powder are uniformly mixed and are made into suspension;Parts by weight are soluble in water for 3~6 parts of chitosan The chitosan solution that mass concentration is 3~5% is configured to, chitosan solution is added in the suspension in step 4, in temperature To stir 3~4h at 60~70 DEG C, cool down, filtering, drying obtains the 5th powder;
Step 5: it is 350 that the 5th powder obtained in polyacrylamide that parts by weight are 6~7 parts, step 4 is added parts by weight 3~4h is stirred at temperature is 60~65 DEG C in~400 parts of water, is cooled down, filtering, is drying to obtain sewage-treating agent.
4. the preparation method of the sewage-treating agent of various heavy in water can be removed as claimed in claim 3, it is characterised in that The second powder adds in metal salt solution and is placed in reacting under nitrogen or argon gas protection environment in step 3.
5. the preparation method of the sewage-treating agent of various heavy in water can be removed as claimed in claim 3, it is characterised in that Iron ion, ferrous ion, copper ion, the molar ratio of nickel ion are 1 in metal salt solution in step 3:0.2~0.3:0.5~1: 0.4~0.8.
6. the preparation method of the sewage-treating agent of various heavy in water can be removed as claimed in claim 3, it is characterised in that Stir speed (S.S.) is 400~600r/min in step 5.
CN201711298636.9A 2017-12-08 2017-12-08 Sewage-treating agent of various heavy and preparation method thereof in water can be removed Pending CN107954492A (en)

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