CN109721151A - For handling the artificial swamp compounded mix of heavy metal wastewater thereby - Google Patents
For handling the artificial swamp compounded mix of heavy metal wastewater thereby Download PDFInfo
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- CN109721151A CN109721151A CN201910100908.2A CN201910100908A CN109721151A CN 109721151 A CN109721151 A CN 109721151A CN 201910100908 A CN201910100908 A CN 201910100908A CN 109721151 A CN109721151 A CN 109721151A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a kind of for handling the artificial swamp compounded mix of heavy metal wastewater thereby, the compounded mix raw material includes following components by weight: 60-70 parts of flyash, 10-20 parts of cement, 10-20 parts of quick lime, 2-8 parts of gypsum, 8-15 parts of olive pomace, 8-12 parts of olive sawdust, 2-6 parts of nitro humus acid resin, 2, 4, 6- tri-thiol -1, 3, 1-4 parts of 5- triazine trisodium salt, 2-6 parts of magnetic bio charcoal, 1-3 parts of ammonium pyrrolidine dithiocarboxylate chelating cellulose, N, bis- (the 2- mercaptoethyls) -1 of N ' -, 1-3 parts of 3- benzenedicarboxamide, 3-6 parts of beta-cyclodextrin, 4-8 parts of silk gum；The packing specific area is big, adsorption capacity is strong, stable structure, microbial biomass on wet land filler carrier can be effectively increased, artificial wet land system is improved to the processing capacity of sewage, especially counterweight Metal Ions Cd 2+, Cr6+, Cu2+, Mn2+ have extraordinary adsorption effect, moreover it is possible to remove part COD, ammonia nitrogen and phosphorus, and can reduce 30% or more artificial swamp area.
Description
Technical field
The present invention relates to field of waste water treatment, in particular to are filled out for handling the artificial swamp of heavy metal wastewater thereby with compound
Material.
Background technique
Heavy metal pollution is mainly derived from two aspects of mankind's activity and Spontaneous release.It shows according to the study, Pb, Zn and Cu exist
Content in sewage is them respectively 30,40 and 15 times of average content in crustal rock.Spontaneous release mainly includes nature
In general weathering Erosion and colcanism etc. not will cause water body by the heavy metal that natural way enters in water environment
Pollution, but cause plurality of heavy metal pollutant to enter in water environment due to mankind's activity, it not only can be to dynamic in water environment
Plant generates direct harm, more can all generate serious adverse effect to human health and the entire ecological balance, cause nothing
The economy and Ecological Loss that method is estimated.Recently as the continuous development of human industry, heavy metal pollution caused by mankind's activity
Have become main aspect.Heavy metal wastewater thereby greatly mostly from industries such as plating, chemical industry, electrolysis, mining, steel, nonferrous smeltings,
Such as mine hole internal drainage, electroplate factory's plating piece washing water, non-ferrous metals smelting works' dedusting draining, waste-rock yard leaching immersion, non-ferrous metal
Processing factory and steel plant's acid washing water, mill tailings draining, and the industrial water drainages such as medicine, pigment, paint, electrolysis, pesticide.Its
Heavy metal type, existing forms and content are different and different because the industry of discharge heavy metal and production technology, and difference is more aobvious
It writes.Such as Cr, Cd, Hg are mainly from plastics industry；Zn, Ti, Sn etc. are mainly from textile industry；Ni, Cd, Zn, Sb mainly from
Microelectronics industry.As metallic weapon is widely used, this makes in city domestic sewage also containing the weight such as a certain amount of Zn, Cu
Metal, and there are the pollutants such as suspended matter, the heavy metal largely generated by traffic activity in the rainfall runoff in city, these are all
Water environment can be damaged.Often there is handling, water is small, at high cost, energy consumption is high, the scope of application for traditional treatment process
It is small, easily cause the deficiencies of secondary pollution, the process cycle of biological treatment is too long and not easy to control.
Summary of the invention
In view of this, the artificial swamp that the purpose of the present invention is to provide a kind of for handling heavy metal wastewater thereby is filled out with compound
Material, the packing specific area is big, and adsorption capacity is strong, stable structure, improves artificial wet land system to the processing capacity of sewage, especially
It is that counterweight Metal Ions Cd 2+, Cr6+, Cu2+, Mn2+ have extraordinary adsorption effect.
The artificial swamp compounded mix for being used to handle heavy metal wastewater thereby of the invention, the compounded mix raw material is by weight
Part includes following components: 60-70 parts of flyash, 10-20 parts of cement, 10-20 parts of quick lime, 2-8 parts of gypsum, olive pomace 8-
15 parts, 8-12 parts of olive sawdust, 2-6 parts of nitro humus acid resin, 1-4 parts of 2,4,6- tri-thiol -1,3,5- triazine trisodium salt,
2-6 parts of magnetic bio charcoal, 1-3 parts of ammonium pyrrolidine dithiocarboxylate chelating cellulose, N, bis- (2- the mercaptoethyl) -1,3- benzene of N ' -
1-3 parts of diformamide, 3-6 parts of beta-cyclodextrin, 4-8 parts of silk gum.
Further, including 65 parts of flyash, 15 parts of cement, 15 parts of quick lime, 4 parts of gypsum, 12 parts of olive pomace, oily olive
10 parts of olive sawdust, 4 parts of nitro humus acid resin, 2 parts of 2,4,6- tri-thiol -1,3,5- triazine trisodium salt, 4 parts of magnetic bio charcoal,
2 parts of ammonium pyrrolidine dithiocarboxylate chelating cellulose, N, bis- 2 parts of (2- the mercaptoethyl) -1,3- benzenedicarboxamides of N ' -, β-ring
4 parts of dextrin, 6 parts of silk gum；
Further, the olive pomace is handled by following manner:
A. the wet pomace of olive is placed in 75-85 DEG C of baking oven and is dried to water content lower than 5% hereinafter, being crushed to partial size and being
0.1-0.3mm is subsequently placed in Soxhlet extractor and uses petroleum ether as degreasing solvent reflux degreasing 7-9h, obtains degreasing olive
Pomace；
B. by the sodium hydroxide solution of degreasing olive pomace and 8% mass fraction temperature be 45-55 DEG C at press feed liquid
It is mixed than 1g:15mL and impregnates 50-70min, then with the speed centrifugal filtration of 3500-4500r/min, collect supernatant and filter
Slag；
C. the ethyl alcohol alcohol precipitation that the concentration of 4 times of volumes is 95% is added after supernatant being concentrated under reduced pressure, is then with concentration
95% ethanol washing is dried under vacuum to constant mass at being 50 DEG C in temperature to neutrality；
D. filter residue is washed to neutrality, heated-air drying is to constant mass at being 50 DEG C in temperature；
E. pulverization process after the product in step c and step d being mixed；
Further, the olive sawdust is handled by following manner: olive sawdust is added in sodium hydroxide solution
It is filtered after impregnating 4-6 hours at room temperature, is then washed with distilled water to neutral and cleaning solution and becomes colorless, be in temperature after filtering
It is 8-10 hours dry at 50-60 DEG C；
Further, the magnetic bio charcoal is prepared by following manner:
F. temperature is that anoxic heats 3.5-4.5 hours at 350-450 DEG C again after the husk of cleaning, drying being crushed, ground
100 meshes；
G. the nitric acid solution that mass concentration is 2mol/L is mixed with the husk in step f by solid-to-liquid ratio 8-12ml:1g,
Temperature is to react 1.5-2.5 hours at 100-120 DEG C, cleans after cooling and is in neutrality and dries to supernatant；
H. by FeCl3·6H2O、FeCl2·4H2Husk in O and step g stirs 20- after being mixed and added into ammonia spirit
Then separation cleaning after forty minutes is added normal propyl alcohol solution and is ultrasonically treated 15-25 minutes, be eventually adding polyethylene glycol stirring 1-3
Hour washed drying；
Further, above-mentioned compounded mix raw material is mixed with sodium hydroxide solution and stirs and be made glutinous shape body,
It is subsequently processed into spherical stickiness particle of several diameters between 5-10mm, by molding haydite in air-drying under natural conditions
It is placed on steam curing in water-bath for 24 hours, after preheating 1.5-2.5 hours at being 35-45 DEG C in temperature, at interval of 0.5h heating 10
DEG C until temperature reach 80 DEG C, last thermostatic curing 12h or more is cooled to room temperature discharging to water bath temperature.
Beneficial effects of the present invention: the artificial swamp compounded mix for being used to handle heavy metal wastewater thereby of the invention, this is filled out
Expect large specific surface area, adsorption capacity is strong, stable structure, can effectively increase microbial biomass on wet land filler carrier, improves artificial
Wet land system has extraordinary absorption to the processing capacity of sewage, especially counterweight Metal Ions Cd 2+, Cr6+, Cu2+, Mn2+
Effect, moreover it is possible to remove part COD, ammonia nitrogen and phosphorus, and 30% or more artificial swamp area can be reduced.
Specific embodiment
Embodiment one
The artificial swamp compounded mix for being used to handle heavy metal wastewater thereby of the present embodiment, the compounded mix raw material is by weight
Measuring part includes following components: 60 parts of flyash, 10 parts of cement, 10 parts of quick lime, 2 parts of gypsum, 8 parts of olive pomace, olive
8 parts of sawdust, 2 parts of nitro humus acid resin, 1 part of 2,4,6- tri-thiol -1,3,5- triazine trisodium salt, 2 parts of magnetic bio charcoal, pyrroles
1 part of alkane dithiocarbonic acid ammonium chelating cellulose, N, bis- 1 part of (2- the mercaptoethyl) -1,3- benzenedicarboxamides of N ' -, beta-cyclodextrin 3
Part, 4 parts of silk gum；
The olive pomace is handled by following manner:
A. the wet pomace of olive is placed in 75 DEG C of baking ovens and is dried to water content lower than 5% hereinafter, being crushed to partial size and being
0.1mm is subsequently placed in Soxhlet extractor and uses petroleum ether as degreasing solvent reflux degreasing 7h, obtains degreasing olive pomace；
B. by the sodium hydroxide solution of degreasing olive pomace and 8% mass fraction temperature be 45 DEG C at press solid-liquid ratio
50min is impregnated in 1g:15mL mixing, then with the speed centrifugal filtration of 3500r/min, collects supernatant and filter residue；
C. the ethyl alcohol alcohol precipitation that the concentration of 4 times of volumes is 95% is added after supernatant being concentrated under reduced pressure, is then with concentration
95% ethanol washing is dried under vacuum to constant mass at being 50 DEG C in temperature to neutrality；
D. filter residue is washed to neutrality, heated-air drying is to constant mass at being 50 DEG C in temperature；
E. pulverization process after the product in step c and step d being mixed；
The olive sawdust is handled by following manner: olive sawdust being added in sodium hydroxide solution and is soaked at room temperature
Bubble filters after 4 hours, is then washed with distilled water to neutral and cleaning solution and becomes colorless, dry at being 50 DEG C in temperature after filtering
8 hours；
The magnetic bio charcoal is prepared by following manner:
F. temperature is that anoxic heats 3.5 hours at 350 DEG C again after the husk of cleaning, drying being crushed, and grinding sieves with 100 mesh sieve；
G. the nitric acid solution that mass concentration is 2mol/L is mixed with the husk in step f by solid-to-liquid ratio 8ml:1g, in temperature
Degree is to react 1.5 hours at 100 DEG C, cleans after cooling and is in neutrality and dries to supernatant；
H. by FeCl3·6H2O、FeCl2·4H2Husk in O and step g stirs 20 points after being mixed and added into ammonia spirit
Separation cleaning after clock, then be added normal propyl alcohol solution be ultrasonically treated 15 minutes, be eventually adding polyethylene glycol stir 1 hour it is washed
Drying；
Above-mentioned compounded mix raw material is mixed with sodium hydroxide solution and stirs and be made glutinous shape body, is then processed
At spherical stickiness particle of several diameters between 5mm, molding haydite is placed on water-bath in air-dried under natural conditions for 24 hours
Steam curing in pot, after being preheated 1.5 hours at being 35 DEG C in temperature, at interval of 10 DEG C of 0.5h heating until temperature reaches 80 DEG C,
Last thermostatic curing 12h or more, is cooled to room temperature discharging to water bath temperature, and granulated filler is made.
Embodiment two
The artificial swamp compounded mix for being used to handle heavy metal wastewater thereby of the present embodiment, the compounded mix raw material is by weight
Measuring part includes following components: 70 parts of flyash, 20 parts of cement, 20 parts of quick lime, 8 parts of gypsum, 15 parts of olive pomace, olive
12 parts of sawdust, 6 parts of nitro humus acid resin, 4 parts of 2,4,6- tri-thiol -1,3,5- triazine trisodium salt, 6 parts of magnetic bio charcoal, pyrrole
Cough up 3 parts of alkane dithiocarbonic acid ammonium chelating cellulose, N, bis- 3 parts of (2- the mercaptoethyl) -1,3- benzenedicarboxamides of N ' -, β-ring paste
6 parts, 8 parts of silk gum of essence；
The olive pomace is handled by following manner:
A. the wet pomace of olive is placed in 75-85 DEG C of baking oven and is dried to water content lower than 5% hereinafter, being crushed to partial size and being
0.3mm is subsequently placed in Soxhlet extractor and uses petroleum ether as degreasing solvent reflux degreasing 7-9h, obtains degreasing olea europaea fruit
Slag；
B. by the sodium hydroxide solution of degreasing olive pomace and 8% mass fraction temperature be 55 DEG C at press solid-liquid ratio
70min is impregnated in 1g:15mL mixing, then with the speed centrifugal filtration of 4500r/min, collects supernatant and filter residue；
C. the ethyl alcohol alcohol precipitation that the concentration of 4 times of volumes is 95% is added after supernatant being concentrated under reduced pressure, is then with concentration
95% ethanol washing is dried under vacuum to constant mass at being 50 DEG C in temperature to neutrality；
D. filter residue is washed to neutrality, heated-air drying is to constant mass at being 50 DEG C in temperature；
E. pulverization process after the product in step c and step d being mixed；
The olive sawdust is handled by following manner: olive sawdust being added in sodium hydroxide solution and is soaked at room temperature
Bubble filters after 6 hours, is then washed with distilled water to neutral and cleaning solution and becomes colorless, dry at being 60 DEG C in temperature after filtering
10 hours；
The magnetic bio charcoal is prepared by following manner:
F. temperature is that anoxic heats 4.5 hours at 450 DEG C again after the husk of cleaning, drying being crushed, and grinding sieves with 100 mesh sieve；
G. the nitric acid solution that mass concentration is 2mol/L is mixed with the husk in step f by solid-to-liquid ratio 12ml:1g, in temperature
Degree is to react 2.5 hours at 120 DEG C, cleans after cooling and is in neutrality and dries to supernatant；
H. by FeCl3·6H2O、FeCl2·4H2Husk in O and step g stirs 40 points after being mixed and added into ammonia spirit
Separation cleaning after clock, then be added normal propyl alcohol solution be ultrasonically treated 25 minutes, be eventually adding polyethylene glycol stir 3 hours it is washed
Drying；
Above-mentioned compounded mix raw material is mixed with sodium hydroxide solution and stirs and be made glutinous shape body, is then processed
At spherical stickiness particle of several diameters between 10mm, molding haydite is placed on water in air-dried under natural conditions for 24 hours
Steam curing in bath after preheating 2.5 hours at being 45 DEG C in temperature, heats up 10 DEG C until temperature reaches 80 at interval of 0.5h
DEG C, last thermostatic curing 12h or more is cooled to room temperature discharging to water bath temperature, and granulated filler is made.
Embodiment three
The artificial swamp compounded mix for being used to handle heavy metal wastewater thereby of the present embodiment, the compounded mix raw material is by weight
Measuring part includes following components: 60 parts of flyash, 20 parts of cement, 10 parts of quick lime, 8 parts of gypsum, 8 parts of olive pomace, olive
12 parts of sawdust, 2 parts of nitro humus acid resin, 4 parts of 2,4,6- tri-thiol -1,3,5- triazine trisodium salt, 2 parts of magnetic bio charcoal, pyrrole
Cough up 3 parts of alkane dithiocarbonic acid ammonium chelating cellulose, N, bis- 1 part of (2- the mercaptoethyl) -1,3- benzenedicarboxamides of N ' -, β-ring paste
6 parts, 4 parts of silk gum of essence；
The olive pomace is handled by following manner:
A. the wet pomace of olive is placed in 75 DEG C of baking ovens and is dried to water content lower than 5% hereinafter, being crushed to partial size and being
0.3mm is subsequently placed in Soxhlet extractor and uses petroleum ether as degreasing solvent reflux degreasing 7h, obtains degreasing olive pomace；
B. by the sodium hydroxide solution of degreasing olive pomace and 8% mass fraction temperature be 55 DEG C at press solid-liquid ratio
50min is impregnated in 1g:15mL mixing, then with the speed centrifugal filtration of 4500r/min, collects supernatant and filter residue；
C. the ethyl alcohol alcohol precipitation that the concentration of 4 times of volumes is 95% is added after supernatant being concentrated under reduced pressure, is then with concentration
95% ethanol washing is dried under vacuum to constant mass at being 50 DEG C in temperature to neutrality；
D. filter residue is washed to neutrality, heated-air drying is to constant mass at being 50 DEG C in temperature；
E. pulverization process after the product in step c and step d being mixed；
The olive sawdust is handled by following manner: olive sawdust being added in sodium hydroxide solution and is soaked at room temperature
Bubble filters after 4 hours, is then washed with distilled water to neutral and cleaning solution and becomes colorless, dry at being 60 DEG C in temperature after filtering
8 hours；
The magnetic bio charcoal is prepared by following manner:
F. temperature is that anoxic heats 3.5 hours at 450 DEG C again after the husk of cleaning, drying being crushed, and grinding sieves with 100 mesh sieve；
G. the nitric acid solution that mass concentration is 2mol/L is mixed with the husk in step f by solid-to-liquid ratio 12ml:1g, in temperature
Degree is to react 2.5 hours at 100 DEG C, cleans after cooling and is in neutrality and dries to supernatant；
H. by FeCl3·6H2O、FeCl2·4H2Husk in O and step g stirs 20 points after being mixed and added into ammonia spirit
Separation cleaning after clock, then be added normal propyl alcohol solution be ultrasonically treated 25 minutes, be eventually adding polyethylene glycol stir 1 hour it is washed
Drying；
Above-mentioned compounded mix raw material is mixed with sodium hydroxide solution and stirs and be made glutinous shape body, is then processed
At spherical stickiness particle of several diameters between 10mm, molding haydite is placed on water in air-dried under natural conditions for 24 hours
Steam curing in bath after preheating 2.5 hours at being 35 DEG C in temperature, heats up 10 DEG C until temperature reaches 80 at interval of 0.5h
DEG C, last thermostatic curing 12h or more is cooled to room temperature discharging to water bath temperature, and granulated filler is made.
Example IV
The artificial swamp compounded mix for being used to handle heavy metal wastewater thereby of the present embodiment, the compounded mix raw material is by weight
Measuring part includes following components: 70 parts of flyash, 10 parts of cement, 20 parts of quick lime, 2 parts of gypsum, 15 parts of olive pomace, olive
8 parts of sawdust, 6 parts of nitro humus acid resin, 1 part of 2,4,6- tri-thiol -1,3,5- triazine trisodium salt, 6 parts of magnetic bio charcoal, pyrroles
1-3 parts of alkane dithiocarbonic acid ammonium chelating cellulose, N, bis- 1 part of (2- the mercaptoethyl) -1,3- benzenedicarboxamides of N ' -, β-ring paste
6 parts, 4 parts of silk gum of essence；
The olive pomace is handled by following manner:
A. the wet pomace of olive is set and is dried in 85 DEG C of baking ovens to water content lower than 5% hereinafter, being crushed to partial size and being
0.3mm is subsequently placed in Soxhlet extractor and uses petroleum ether as degreasing solvent reflux degreasing 9h, obtains degreasing olive pomace；
B. by the sodium hydroxide solution of degreasing olive pomace and 8% mass fraction temperature be 45 DEG C at press solid-liquid ratio
70min is impregnated in 1g:15mL mixing, then with the speed centrifugal filtration of 3500r/min, collects supernatant and filter residue；
C. the ethyl alcohol alcohol precipitation that the concentration of 4 times of volumes is 95% is added after supernatant being concentrated under reduced pressure, is then with concentration
95% ethanol washing is dried under vacuum to constant mass at being 50 DEG C in temperature to neutrality；
D. filter residue is washed to neutrality, heated-air drying is to constant mass at being 50 DEG C in temperature；
E. pulverization process after the product in step c and step d being mixed；
The olive sawdust is handled by following manner: olive sawdust being added in sodium hydroxide solution and is soaked at room temperature
Bubble filters after 6 hours, is then washed with distilled water to neutral and cleaning solution and becomes colorless, dry at being 50 DEG C in temperature after filtering
10 hours；
The magnetic bio charcoal is prepared by following manner:
F. temperature is that anoxic heats 4.5 hours at 350 DEG C again after the husk of cleaning, drying being crushed, and grinding sieves with 100 mesh sieve；
G. the nitric acid solution that mass concentration is 2mol/L is mixed with the husk in step f by solid-to-liquid ratio 8ml:1g, in temperature
Degree is to react 1.5 hours at 120 DEG C, cleans after cooling and is in neutrality and dries to supernatant；
H. by FeCl3·6H2O、FeCl2·4H2Husk in O and step g stirs 40 points after being mixed and added into ammonia spirit
Separation cleaning after clock, then be added normal propyl alcohol solution be ultrasonically treated 15 minutes, be eventually adding polyethylene glycol stir 3 hours it is washed
Drying；
Above-mentioned compounded mix raw material is mixed with sodium hydroxide solution and stirs and be made glutinous shape body, is then processed
At spherical stickiness particle of several diameters between 5mm, molding haydite is placed on water-bath in air-dried under natural conditions for 24 hours
Steam curing in pot, after being preheated 1.5 hours at being 45 DEG C in temperature, at interval of 10 DEG C of 0.5h heating until temperature reaches 80 DEG C,
Last thermostatic curing 12h or more, is cooled to room temperature discharging to water bath temperature, and granulated filler is made.
Embodiment five
The artificial swamp compounded mix for being used to handle heavy metal wastewater thereby of the present embodiment, the compounded mix raw material is by weight
Measuring part includes following components: 65 parts of flyash, 10 parts of cement, 20 parts of quick lime, 4 parts of gypsum, 15 parts of olive pomace, olive
8 parts of sawdust, 4 parts of nitro humus acid resin, 1 part of 2,4,6- tri-thiol -1,3,5- triazine trisodium salt, 6 parts of magnetic bio charcoal, pyrroles
2 parts of alkane dithiocarbonic acid ammonium chelating cellulose, N, bis- 3 parts of (2- the mercaptoethyl) -1,3- benzenedicarboxamides of N ' -, beta-cyclodextrin 3
Part, 6 parts of silk gum；
The olive pomace is handled by following manner:
A. the wet pomace of olive is placed in 80 DEG C of baking ovens and is dried to water content lower than 5% hereinafter, being crushed to partial size and being
0.1mm is subsequently placed in Soxhlet extractor and uses petroleum ether as degreasing solvent reflux degreasing 9h, obtains degreasing olive pomace；
B. by the sodium hydroxide solution of degreasing olive pomace and 8% mass fraction temperature be 50 DEG C at press solid-liquid ratio
50min is impregnated in 1g:15mL mixing, then with the speed centrifugal filtration of 4500r/min, collects supernatant and filter residue；
C. the ethyl alcohol alcohol precipitation that the concentration of 4 times of volumes is 95% is added after supernatant being concentrated under reduced pressure, is then with concentration
95% ethanol washing is dried under vacuum to constant mass at being 50 DEG C in temperature to neutrality；
D. filter residue is washed to neutrality, heated-air drying is to constant mass at being 50 DEG C in temperature；
E. pulverization process after the product in step c and step d being mixed；
The olive sawdust is handled by following manner: olive sawdust being added in sodium hydroxide solution and is soaked at room temperature
Bubble filters after 5 hours, is then washed with distilled water to neutral and cleaning solution and becomes colorless, dry at being 50 DEG C in temperature after filtering
10 hours；
The magnetic bio charcoal is prepared by following manner:
F. temperature is that anoxic heats 3.5 hours at 400 DEG C again after the husk of cleaning, drying being crushed, and grinding sieves with 100 mesh sieve；
G. the nitric acid solution that mass concentration is 2mol/L is mixed with the husk in step f by solid-to-liquid ratio 12ml:1g, in temperature
Degree is to react 2.5 hours at 110 DEG C, cleans after cooling and is in neutrality and dries to supernatant；
H. by FeCl3·6H2O、FeCl2·4H2Husk in O and step g stirs 20 points after being mixed and added into ammonia spirit
Separation cleaning after clock, then be added normal propyl alcohol solution be ultrasonically treated 20 minutes, be eventually adding polyethylene glycol stir 1 hour it is washed
Drying；
Above-mentioned compounded mix raw material is mixed with sodium hydroxide solution and stirs and be made glutinous shape body, is then processed
At spherical stickiness particle of several diameters between 7mm, molding haydite is placed on water-bath in air-dried under natural conditions for 24 hours
Steam curing in pot, after being preheated 2.5 hours at being 35 DEG C in temperature, at interval of 10 DEG C of 0.5h heating until temperature reaches 80 DEG C,
Last thermostatic curing 12h or more, is cooled to room temperature discharging to water bath temperature, and granulated filler is made.
Embodiment six
The artificial swamp compounded mix for being used to handle heavy metal wastewater thereby of the present embodiment, the compounded mix raw material is by weight
Measuring part includes following components: including 65 parts of flyash, 15 parts of cement, 15 parts of quick lime, 4 parts of gypsum, 12 parts of olive pomace, oil
10 parts of olive sawdust, 4 parts of nitro humus acid resin, 2 parts of 2,4,6- tri-thiol -1,3,5- triazine trisodium salt, magnetic bio charcoal 4
Part, 2 parts of ammonium pyrrolidine dithiocarboxylate chelating cellulose, N, bis- 2 parts of (2- the mercaptoethyl) -1,3- benzenedicarboxamides of N ' -, β -
4 parts of cyclodextrin, 6 parts of silk gum；
The olive pomace is handled by following manner:
A. the wet pomace of olive is placed in 80 DEG C of baking ovens and is dried to water content lower than 5% hereinafter, being crushed to partial size and being
0.2mm is subsequently placed in Soxhlet extractor and uses petroleum ether as degreasing solvent reflux degreasing 8h, obtains degreasing olive pomace；
B. by the sodium hydroxide solution of degreasing olive pomace and 8% mass fraction temperature be 50 DEG C at press solid-liquid ratio
60min is impregnated in 1g:15mL mixing, then with the speed centrifugal filtration of 4000r/min, collects supernatant and filter residue；
C. the ethyl alcohol alcohol precipitation that the concentration of 4 times of volumes is 95% is added after supernatant being concentrated under reduced pressure, is then with concentration
95% ethanol washing is dried under vacuum to constant mass at being 50 DEG C in temperature to neutrality；
D. filter residue is washed to neutrality, heated-air drying is to constant mass at being 50 DEG C in temperature；
E. pulverization process after the product in step c and step d being mixed；
The olive sawdust is handled by following manner: olive sawdust being added in sodium hydroxide solution and is soaked at room temperature
Bubble filters after 5 hours, is then washed with distilled water to neutral and cleaning solution and becomes colorless, dry at being 55 DEG C in temperature after filtering
9 hours；
The magnetic bio charcoal is prepared by following manner:
F. temperature is that anoxic heats 4 hours at 400 DEG C again after the husk of cleaning, drying being crushed, and grinding sieves with 100 mesh sieve；
G. the nitric acid solution that mass concentration is 2mol/L is mixed with the husk in step f by solid-to-liquid ratio 10ml:1g, in temperature
Degree is to react 2 hours at 110 DEG C, cleans after cooling and is in neutrality and dries to supernatant；
H. by FeCl3·6H2O、FeCl2·4H2Husk in O and step g stirs 30 points after being mixed and added into ammonia spirit
Separation cleaning after clock, then be added normal propyl alcohol solution be ultrasonically treated 20 minutes, be eventually adding polyethylene glycol stir 2 hours it is washed
Drying；
Above-mentioned compounded mix raw material is mixed with sodium hydroxide solution and stirs and be made glutinous shape body, is then processed
At spherical stickiness particle of several diameters between 7mm, molding haydite is placed on water-bath in air-dried under natural conditions for 24 hours
Steam curing in pot after preheating 2 hours at being 40 DEG C in temperature, heats up 10 DEG C until temperature reaches 80 DEG C, most at interval of 0.5h
Thermostatic curing 12h or more afterwards is cooled to room temperature discharging to water bath temperature, and granulated filler is made.
Compounded mix of the invention achieves ideal effect in artificial wetland treatment industrial wastewater.In 18 months fortune
In row monitoring process, the removal rate of Cd2+, Cr6+, Cu2+, Mn2+ are up to 99.4%, 99.2%, 95.5% and 96.8% or more,
COD、BOD5, NH3-N and TP average removal rate be up to 85.6%, 83.2%, 93.2% and 81.8% or more respectively.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (6)
1. a kind of for handling the artificial swamp compounded mix of heavy metal wastewater thereby, it is characterised in that: the compounded mix raw material
It by weight include following components: 60-70 parts of flyash, 10-20 parts of cement, 10-20 parts of quick lime, 2-8 parts of gypsum, olive
8-15 parts of pomace, 8-12 parts of olive sawdust, 2-6 parts of nitro humus acid resin, 2,4,6- tri-thiol -1,3,5- triazine trisodium salt
1-4 parts, 2-6 parts of magnetic bio charcoal, 1-3 parts of ammonium pyrrolidine dithiocarboxylate chelating cellulose, N, N '-bis- (2- mercaptoethyls)-
1-3 parts of 1,3- benzenedicarboxamide, 3-6 parts of beta-cyclodextrin, 4-8 parts of silk gum.
2. according to claim 1 for handling the artificial swamp compounded mix of heavy metal wastewater thereby, it is characterised in that: packet
It is rotten to include 65 parts of flyash, 15 parts of cement, 15 parts of quick lime, 4 parts of gypsum, 12 parts of olive pomace, 10 parts of olive sawdust, nitro
Grow 4 parts of acid resin, 2 parts of 2,4,6- tri-thiol -1,3,5- triazine trisodium salt, 4 parts of magnetic bio charcoal, ammonium pyrrolidine dithiocarboxylate
2 parts of chelating cellulose, N, bis- 2 parts of (2- the mercaptoethyl) -1,3- benzenedicarboxamides of N ' -, 4 parts of beta-cyclodextrin, 6 parts of silk gum.
3. according to claim 1 for handling the artificial swamp compounded mix of heavy metal wastewater thereby, it is characterised in that: institute
Olive pomace is stated to handle by following manner:
A. the wet pomace of olive is placed in 75-85 DEG C of baking oven and is dried to water content lower than 5% hereinafter, being crushed to partial size is 0.1-
0.3mm is subsequently placed in Soxhlet extractor and uses petroleum ether as degreasing solvent reflux degreasing 7-9h, obtains degreasing olea europaea fruit
Slag；
B. by the sodium hydroxide solution of degreasing olive pomace and 8% mass fraction temperature be 45-55 DEG C at press solid-liquid ratio 1g:
50-70min is impregnated in 15mL mixing, then with the speed centrifugal filtration of 3500-4500r/min, collects supernatant and filter residue；
C. the ethyl alcohol alcohol precipitation that the concentration of 4 times of volumes is 95% is added after supernatant being concentrated under reduced pressure, is then 95% with concentration
Ethanol washing is dried under vacuum to constant mass at being 50 DEG C in temperature to neutrality；
D. filter residue is washed to neutrality, heated-air drying is to constant mass at being 50 DEG C in temperature；
E. pulverization process after the product in step c and step d being mixed.
4. the heavy metal chelating agent according to claim 3 for wastewater treatment, it is characterised in that: the olive sawdust
It is handled by following manner: olive sawdust being added in sodium hydroxide solution after impregnating 4-6 hours at room temperature and filtered, then used
Distillation water washing to neutral and cleaning solution becomes colorless, 8-10 hours dry at being 50-60 DEG C in temperature after filtering.
5. the heavy metal chelating agent according to claim 4 for wastewater treatment, it is characterised in that: the magnetic bio charcoal
It is prepared by following manner:
F. temperature is that anoxic heats 3.5-4.5 hours at 350-450 DEG C again after the husk of cleaning, drying being crushed, ground 100
Mesh；
G. the nitric acid solution that mass concentration is 2mol/L is mixed with the husk in step f by solid-to-liquid ratio 8-12ml:1g, in temperature
It is to be reacted 1.5-2.5 hours at 100-120 DEG C, is cleaned after cooling and be in neutrality and dry to supernatant；
H. by FeCl3·6H2O、FeCl2·4H2Husk in O and step g stirs 20-40 minutes after being mixed and added into ammonia spirit
Then separation cleaning afterwards is added normal propyl alcohol solution and is ultrasonically treated 15-25 minutes, be eventually adding polyethylene glycol and stir 1-3 hours warps
Washing and drying.
6. it is according to claim 1 for handling the preparation method of the artificial swamp compounded mix of heavy metal wastewater thereby,
Be characterized in that: above-mentioned compounded mix raw material being mixed with sodium hydroxide solution and stirs and be made glutinous shape body, then plus
Spherical stickiness particle of the work at several diameters between 5-10mm, by molding haydite in air-dried postposition for 24 hours under natural conditions
The steam curing in water-bath, temperature be 35-45 DEG C at preheat 1.5-2.5 hour after, at interval of 0.5h heating 10 DEG C up to
Temperature reaches 80 DEG C, and last thermostatic curing 12h or more is cooled to room temperature discharging to water bath temperature.
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| CN110862187A (en) * | 2019-08-16 | 2020-03-06 | 重庆工程职业技术学院 | Artificial wetland for treating industrial wastewater |
| CN113060823A (en) * | 2021-03-24 | 2021-07-02 | 中国科学院生态环境研究中心 | Constructed wetland filler and preparation method thereof |
| CN113173765A (en) * | 2021-04-16 | 2021-07-27 | 浙江尼可环保科技有限公司 | Wetland composite filler applied to treatment of rural domestic sewage and preparation method thereof |
| US11685854B1 (en) | 2022-09-20 | 2023-06-27 | King Fahd University Of Petroleum And Minerals | Carbonation-resistant cementitious blend containing olive waste |
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| CN113060823A (en) * | 2021-03-24 | 2021-07-02 | 中国科学院生态环境研究中心 | Constructed wetland filler and preparation method thereof |
| CN113060823B (en) * | 2021-03-24 | 2021-12-14 | 中国科学院生态环境研究中心 | Constructed wetland filler and preparation method thereof |
| CN113173765A (en) * | 2021-04-16 | 2021-07-27 | 浙江尼可环保科技有限公司 | Wetland composite filler applied to treatment of rural domestic sewage and preparation method thereof |
| US11685854B1 (en) | 2022-09-20 | 2023-06-27 | King Fahd University Of Petroleum And Minerals | Carbonation-resistant cementitious blend containing olive waste |
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