CN110479226A - A kind of clay mineral/agricultural abandoned biomass compound sewage inorganic agent, preparation method and application - Google Patents
A kind of clay mineral/agricultural abandoned biomass compound sewage inorganic agent, preparation method and application Download PDFInfo
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- CN110479226A CN110479226A CN201910816199.8A CN201910816199A CN110479226A CN 110479226 A CN110479226 A CN 110479226A CN 201910816199 A CN201910816199 A CN 201910816199A CN 110479226 A CN110479226 A CN 110479226A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention discloses a kind of clay mineral/agricultural abandoned biomass compound sewage inorganic agent, preparation method and applications.Using the naturally occurring clay mineral of nature, renewable agricultural abandoned biomass, organic binder as raw material, after ball milling mixes, is ultra-fine, the wetting of heating water and the obtained slurry of aging processing；After mill mixing, compression molding, drying, broken, classification processing, clay mineral/biomass combined sewage-treating agent is made.Gained sewage-treating agent of the invention has the ability of Adsorption simultaneously to organic dyestuff, heavy metal ion, fluorine ion etc..Method provided by the invention has the characteristics that rich inexpensive amount, green low-carbon using natural clay mineral and agricultural abandoned biomass as compound sewage inorganic agent prepared by raw material, with the pollution treatment, performance efficiency of giving up, preparation method has simple process, environmental protection and energy saving, is easy to the advantages such as volume production, and applying in sewage treatment has broad prospect of application.
Description
Technical field
The invention belongs to mineral-base composite material and sewage treatment fields, and in particular to a kind of clay mineral/agricultural are discarded
Biomass combined sewage-treating agent, preparation method and application.
Background technique
Social economy's fast-developing (industrialization, urbanization) brings the environmental problems such as serious water pollution, water pollution processing
It is global general character project with prevention and treatment science and technology, the even more great demand of China at this stage.But according to " major river valley water prevention and cure of pollution are advised
Draw ", national surface water has nearly 10% section water quality for bad V class, and the pollution such as nitrogen, phosphorus, heavy metal is increasingly prominent, even micro
Heavy metal all has grave danger (Environ. Technol. 2018,11,187) to human health, aquatic system and environment.
Ministry of Industry and Information's " about instruction for accelerating that environmentally friendly equipment manufacture is promoted to develop " requires emphasis to research and develop " new and effective water process material
Material and medicament ", " restoration of the ecosystem, environmentally friendly nano material and medicament " develop multi-pollutant collaboration processing, advanced treatment technologies.
As it can be seen that research and development are efficient, the water soluble contaminants Adsorption new composite adsorbent of low cost, ecological, environmental protective, meet development
Trend agrees with the great demand of country.
Water soluble contaminants include that the types such as heavy metal ion, organic dyestuff, agriculture medicine intermediate and remnant are complicated more
It is sample, distinct, it often simultaneously and deposits, is a challenge to purification treatment technology.Common processing method has the precipitation method, burns
Method, flocculence, Coagulation Method, ion-exchange, hyperfiltration, membrane filter method, electrochemistry, photochemistry, advanced oxidation processes, bioanalysis
Deng (App. Clay Sci. 2016,123,239), but these methods some the disadvantage is that: removal efficiency is low, sludge yield
Height, low cost, the generation of harmful by-products, and will use a large amount of chemical article (J. Environ. Manage. 2016,
179,20).Adsorption method be the highest sewage water treatment method of current cost performance (Environ. Technol.2009,6,
583), core technology bottleneck is the design and magnanimity preparation of efficient, inexpensive, ecological friendly adsorbent.Common absorption
Agent has a synthetic polymer (such as PAM), clay, biomass, but that there are particles is big, have a single function, adsorbance is low, environment phase for majority
The problems such as capacitive is poor, it is difficult to which meet volume is big and the complicated and diversified water process of pollution sources requires.In addition, the chemical industry industrially used closes
It is more expensive at the price of adsorbent, increase cost of sewage disposal.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of clay mineral/agricultural abandoned biomass is compound
Sewage-treating agent, preparation method and application: with inexpensive amount, rich, ecological, environmental protective lamellar clay, agricultural-forestry biomass etc. are naturally provided
Source is raw material, by the asymmetric ultra-fine removing of the blocks such as clay, biomass at two-dimentional clay nano piece and one-dimensional biomass nano
Fiber, and clay nano piece and biomass nano fiber hydridization are embedded in, it is more to construct " clay nano piece/biomass nano fiber "
Level hybrid nanostructure；By the synergistic effect between polynary composition, multilevel structure, various functional group, disposable Adsorption
Complicated and diversified soluble pollutants in sewage.The present invention, which has, measures rich inexpensive, ecological, environmental protective, good sewage processing effect, preparation
The advantages such as simple process, easy mass production.
To achieve the above object, the invention adopts the following technical scheme: with the naturally occurring clay mineral of nature, can be again
Raw agricultural abandoned biomass, organic binder are raw material, and after ball milling mixes, is ultra-fine, heating water is soaked and aging processing is made
Slurry；After mill mixing, compression molding, drying, broken, classification processing, it is made at clay mineral/biomass combined sewage
Manage agent.A kind of clay mineral/agricultural abandoned biomass compound sewage inorganic agent and preparation method thereof, comprising the following steps:
(1) using agricultural abandoned biomass, clay mineral, binder as raw material, by clay mineral, agricultural abandoned biomass, bonding
The mass ratio of agent=(1 ~ 5): 10:(2 ~ 6) ball milling；
(2) hot water being added in the resulting mixed powder of the step (1), be thoroughly mixed uniformly, the temperature of hot water is 40 ~
95 DEG C, the mass ratio of hot water and mixed powder is (2.5 ~ 5): 1；
(3) step (2) resulting material is sealed to aging processing under the conditions of being placed on set temperature, aging condition is in 40 ~ 100o
C keeps the temperature 5 ~ 48 h；
(4) mixed slurry obtained by step (3) is through mixing, tabletting, drying；
(5) for the resulting dry block of step (4) through broken, sieving, classification, being made by clay mineral, biomass is main component
Compound sewage inorganic agent.
As a preferred embodiment of the above technical solution, the agricultural abandoned biomass is jute stalk and leaf, stalk, corncob, sugarcane
The mixture of one or more of slag, rice husk, pericarp, algae arbitrary proportion.
As a preferred embodiment of the above technical solution, the clay mineral is bentonite, kaolin, concave convex rod, sepiolite, illiteracy
The mixture of one or more of de- stone, galapectite, vermiculite, smectite, palygorskite, illite arbitrary proportion.
As a preferred embodiment of the above technical solution, the binder is starch, protein, animal glue, Sodium Alginate, carboxymethyl
Sodium cellulosate, polyacrylamide, Sodium Polyacrylate, polyvinyl pyridine salt, polyethyleneimine, polydimethyl diallyl ammonium chloride
One or more of arbitrary proportion mixture.
As a preferred embodiment of the above technical solution, the abrading-ball used be alumina balls, it is zirconia ball, mullite ball, stainless
The mass ratio (3 ~ 6) of the mixture of one or more kinds of arbitrary proportions of steel ball, abrading-ball and material: 1, ball radius is 3 ~ 15
Mm, rotational speed of ball-mill are 50 ~ 600 rpm, and Ball-milling Time is 1 ~ 20 h.
As a preferred embodiment of the above technical solution, described be kneaded, tabletting is using open mill processing, the front wheel rotation speed 5 of open mill ~
20 rpm, 5 ~ 20 rpm of rear wheel rotation speed of open mill, 40 ~ 100 oC of front-wheel temperature, rear-wheel 40 ~ 100oC of temperature, front and back wheel spacing
0.5~5mm。
As a preferred embodiment of the above technical solution, the drying refers in 80 ~ 150 DEG C of dry 2 ~ 16 h, moisture content (2 ~
10)%。
As a preferred embodiment of the above technical solution, after being crushed, being sieved in the step (5), gained composite treating agent granularity model
It encloses for 0.1 ~ 1 mm.
Clay mineral made from above-mentioned preparation method/agricultural abandoned biomass compound sewage inorganic agent.
Above-mentioned clay mineral/agricultural abandoned biomass compound sewage inorganic agent answering in adsorbing heavy metal ions in sewage
With the preferred copper ion of heavy metal ion.
The application of above-mentioned clay mineral/agricultural abandoned biomass compound sewage inorganic agent organic dyestuff in absorption effluent,
The preferred methylene blue of organic dyestuff.
The invention has the following advantages:
The present invention combines the low-dimensional synusia or fibre structure of renewable biomass functional group abundant and natural clay mineral,
It is acted synergistically using them, promotes compound to the harmful ions such as organic dyestuff, heavy metal ion, fluorine ion while Adsorption
Ability, have adaptability more stronger than existing business sewage-treating agent.
In addition, the compound dirt that method provided by the invention is prepared using natural clay mineral and agricultural abandoned biomass as raw material
Water treatment agent has the characteristics that rich inexpensive amount, green low-carbon, with the pollution treatment, performance efficiency of giving up, and preparation method has simple process, ring
It protects energy conservation, be easy to the advantages such as volume production, applying in sewage treatment has broad prospect of application.
The present invention breaches the rich New Type Water Treatment Chemicals design of efficient ecological, inexpensive amount and preparation key technology, realizes layer
The sustainable development of the higher value application of the natural resources such as shape clay, biomass and " with pollution treatment of giving up " green low-carbon water treatment technology
The theoretical system and case for improving mineral material preparation and application are enriched in exhibition.
Detailed description of the invention
Fig. 1 is the experiment flow figure of embodiment preparation.
Fig. 2 is the XRD diagram of sample obtained by embodiment 1；
Fig. 3 is the SEM figure of sample obtained by embodiment 1；
Fig. 4 is the XRD diagram of sample obtained by embodiment 2；
Fig. 5 is the SEM figure of sample obtained by embodiment 2；
Fig. 6 is the XRD diagram of sample obtained by embodiment 3；
Fig. 7 is the SEM figure of sample obtained by embodiment 3；
Fig. 8 is the XRD diagram of sample obtained by embodiment 4；
Fig. 9 is the SEM figure of sample obtained by embodiment 4；
Figure 10 is the XRD diagram of sample obtained by embodiment 5；
Figure 11 is the SEM figure of sample obtained by embodiment 5；
Figure 12 is the XRD diagram of sample obtained by embodiment 6；
Figure 13 is the SEM figure of sample obtained by embodiment 6.
Figure 14 is compound sewage inorganic agent to Cu2+The performance map of absorption.
Figure 15 is unmodified raw material to Cu2+The performance map of absorption.
Figure 16 is performance map of the compound sewage inorganic agent to methylene blue adsorption number.
Figure 17 is performance map of the unmodified raw material to methylene blue adsorption number.
Figure 18 is sample obtained by embodiment 2 to different Cu2+The influence of concentration absorption property and removal rate.
Figure 19 is influence of the sample to different methylene blue concentration absorption properties and removal rate obtained by embodiment 2.
Specific embodiment
In order to better understand the present invention, below by with jute, bentonite, kaolin, concave convex rod, anion pp
Amide etc. be raw material embodiment the present invention is further described, embodiment be served only for explain the present invention, will not be to structure of the present invention
At any restriction.
Embodiment 1
Jute powder (leaf powder) 15 g, 4.5 g of bentonite, 3 g of anionic polyacrylamide (APAM) are mixed and are put into poly- four
In vinyl fluoride ball grinder, alumina balls (by quality ratio, the big ball 20% of 10 mm of diameter, ball 50%, diameter 3mm are small in 5 mm of diameter
Ball 30%) with the mass ratio of compound material be 6:1, the revolving speed of ball-milling treatment is 500 rpm, after 4 h of ball milling mixed-powder.It will
Above-mentioned mixed-powder is put into agate mortar, and the 50oC warm water that 90 g are added stirs evenly, then is wrapped up with preservative film, is put into baking oven
Interior aging 10 h of 50oC obtains composite mortar.The composite mortar is put into open mill and carries out mixing process, the front-wheel of open mill
4 rpm of revolving speed, 2 rpm of rear wheel rotation speed, front and rear wheel temperature are 50oC, 1 mm of front and back wheel spacing；It is pressed into piece after being sufficiently kneaded,
Clay mineral/biomass combined is obtained through 12 h of 80oC oven drying.Then, composite sheet crosses 60 purposes after broken crusher machine
Sieve, screenings are clay mineral/biomass combined sewage-treating agent.
Gained clay mineral/biomass combined sewage-treating agent Adsorption of Cu2+Condition are as follows: 2 g/L of preliminary examination concentration, sewage treatment
Agent dosage 2 g/L, pH=5, temperature 55oC, 60 min of adsorption time test adsorbance, are as a result detailed in Figure 14.
Gained clay mineral/biomass combined sewage-treating agent absorption methylene blue condition are as follows: 500 mg/ of preliminary examination concentration
L, sewage-treating agent dosage 1.6 g/L, pH=6, temperature 60oC, 150 min of adsorption time test adsorbance.
Fig. 1 is the preparation flow figure of experiment, describes the preparation process of compound sewage inorganic agent in detail.
Fig. 2 is roundpod jute leaf powder, bentonite, roundpod jute leaf powder/bentonite compound sewage inorganic agent XRD, compound sewage processing
The XRD diagram of agent substantially and it is bentonitic matches, but the intensity at peak is relatively low, this is jute powder intercalation compound bentonite and reduces
The reason of its long-range order degree.
Fig. 3 is jute powder/bentonite compound sewage inorganic agent SEM figure, as can be seen from the figure bentonitic surface packet
Jute powder is wrapped up in, interlayer also has jute powder, and the comparison that this structure illustrates that bentonite and jute powder combine is close, compound
Sewage-treating agent Adsorption of Cu2+Or its synergistic effect is played to jute powder and bentonite when methylene blue there is promotion.
1 gained compound sewage inorganic agent of embodiment is to Cu2+The performance of absorption is as shown in figure 14, it can be seen that embodiment 1 produces
Object is to Cu2+Adsorbance be 257.3 mg/g.
Figure 15 is unmodified raw material to Cu2+The performance map of absorption, in conjunction with embodiment 1 in Figure 14 and embodiment 7 to Cu2+
Adsorbance, it can be deduced that conclusion, compound sewage inorganic agent is to Cu2+Adsorbance be much larger than unmodified raw material adsorbance,
And the compound sewage inorganic agent after bentonite is added is to Cu2+Large amount of adsorption in bentonite compound sewage inorganic agent is not added
The adsorbance of (i.e. embodiment 7).
1 gained compound sewage inorganic agent of embodiment is as shown in figure 16 to the performance of methylene blue adsorption number, it can be seen that implements
1 product of example is 155 mg/g to the adsorbance of methylene blue.
Figure 17 is performance map of the unmodified raw material to methylene blue adsorption number, right in conjunction with embodiment 1 in Figure 16 and embodiment 7
The adsorbance of methylene blue, it can be deduced that conclusion, compound sewage inorganic agent are much larger than unmodified sample to the adsorbance of methylene blue
The adsorbance of product, and the compound sewage inorganic agent after bentonite is added to the large amount of adsorption of methylene blue in bentonite is not added
The adsorbance of compound sewage inorganic agent.
Embodiment 2
Jute powder (leaf powder) 15 g, 4.5 g of bentonite, 9 g of anionic polyacrylamide (APAM) are put into polytetrafluoroethylene (PTFE)
Ball grinder in, alumina balls (by quality ratio, the big ball accounting 20% of 10 mm of diameter, 50 accounting % of ball, diameter in 5 mm of diameter
3mm bead accounting 30%) it with the mass ratio of compound material is 6:1, the revolving speed of ball mill is 500 rpm, 4 h of ball milling, after ball milling
To mixed-powder.Other processing methods are the same as embodiment 1.
Gained clay mineral/biomass combined sewage-treating agent Adsorption of Cu2+Condition are as follows: 2 g/L of preliminary examination concentration, sewage treatment
Agent dosage 2 g/L, pH=5, temperature 55oC, 60 min of adsorption time test adsorbance.
Different Cu2+The condition that concentration influences clay mineral/biomass combined sewage-treating agent absorption property are as follows: preliminary examination is dense
Spend 1 g/L, 1.2 g/L, 1.4 g/L, 1.6 g/L, 1.8 g/L, 2 g/L, 2.2 g/L, sewage-treating agent dosage 2 g/L, pH=
5, temperature 55oC, 60 min of adsorption time test adsorbance, are as a result detailed in Figure 18.
Gained clay mineral/biomass combined sewage-treating agent absorption methylene blue condition are as follows: 500 mg/ of preliminary examination concentration
L, sewage-treating agent dosage 1.6 g/L, pH=6, temperature 60oC, 150 min of adsorption time test adsorbance.
The condition that different methylene blue concentration influence clay mineral/biomass combined sewage-treating agent absorption property are as follows:
100 mg/L of preliminary examination concentration, 200 mg/L, 300 mg/L, 400 mg/L, 500 mg/L, 600 mg/L, 700 mg/L, at sewage
Agent dosage 1.6 g/L, pH=6, temperature 60oC, 150 min of adsorption time are managed, adsorbance is tested, is as a result detailed in Figure 19.
Fig. 4 is roundpod jute leaf powder, bentonite, roundpod jute leaf powder/bentonite compound sewage inorganic agent XRD, compound sewage processing
The XRD diagram of agent matches with bentonitic substantially.
Fig. 5 is jute powder/bentonite compound sewage inorganic agent SEM figure, as can be seen from the figure bentonitic surface packet
Jute powder is wrapped up in, interlayer also has jute powder, and the comparison that this structure illustrates that bentonite and jute powder combine is close, compound
Sewage-treating agent Adsorption of Cu2+Or its synergistic effect is played to jute powder and bentonite when methylene blue there is promotion.
2 gained compound sewage inorganic agent of embodiment is to Cu2+The performance of absorption is as shown in figure 14, it can be seen that embodiment 2 produces
Object is to Cu2+Adsorbance be 327.3 mg/g
Figure 15 is unmodified raw material to Cu2+The performance map of absorption, in conjunction with embodiment 2 in Figure 14 and embodiment 7 to Cu2+Suction
Attached amount, it can be deduced that conclusion, compound sewage inorganic agent is to Cu2+Adsorbance be much larger than the adsorbances of unmodified raw material, and add
Enter the compound sewage inorganic agent after bentonite to Cu2+Large amount of adsorption in the absorption that bentonite compound sewage inorganic agent is not added
Amount.
2 gained compound sewage inorganic agent of embodiment is as shown in figure 16 to methylene blue adsorption number performance, it can be seen that embodiment 2
Product is 169.4 mg/g to the adsorbance of methylene blue.
Figure 17 is performance map of the unmodified raw material to methylene blue adsorption number, right in conjunction with embodiment 2 in Figure 16 and embodiment 7
The adsorbance of methylene blue, it can be deduced that conclusion, compound sewage inorganic agent are much larger than unmodified sample to the adsorbance of methylene blue
The adsorbance of product, and the compound sewage inorganic agent after bentonite is added to the large amount of adsorption of methylene blue in bentonite is not added
The adsorbance of compound sewage inorganic agent.
Figure 18 is 2 couples of difference Cu of embodiment2+The influence of concentration absorption property and removal rate, as we know from the figure with Cu2+It is dense
The increase compound sewage inorganic agent of degree is to Cu2+Adsorbance be gradually increased then close to balance, and its corresponding removal rate is gradually
It reduces.
Figure 19 is the influence of 2 pairs of embodiment different methylene blue concentration absorption properties and removal rate, as we know from the figure with
The increase compound sewage inorganic agent of methylene blue concentration is gradually increased then close to balance the adsorbance of methylene blue, and opposite
Its removal rate is answered to gradually decrease.
Embodiment 3
By 15 g(bar powder of jute powder), 7.5 g of kaolin, 9 g of anionic polyacrylamide (APAM) be put into polytetrafluoroethylene (PTFE)
In ball grinder, alumina balls (by quality ratio, the big ball accounting 20% of 10 mm of diameter, ball accounting 50%, diameter 3mm in 5 mm of diameter
Bead accounting 30%) it with the mass ratio of compound material is 6:1, the revolving speed of ball mill is 500 rpm, 4 h of ball milling, is obtained after ball milling
Mixed-powder.Other processing methods are the same as embodiment 1.
Gained clay mineral/biomass combined sewage-treating agent Adsorption of Cu2+, methylene blue condition with embodiment 1.
Fig. 6 is jute stalk powder, kaolin, jute stalk powder/kaolin compound sewage inorganic agent XRD, compound sewage processing
The XRD diagram of agent matches with kaolinic substantially.
Fig. 7 is jute stalk powder/kaolin composite material sewage-treating agent SEM figure, as can be seen from the figure kaolinic
Jute powder has been wrapped up on surface, and interlayer also has jute powder, and the comparison that this structure illustrates that kaolin and jute powder combine is close,
In compound sewage inorganic agent Adsorption of Cu2+Or its synergistic effect is played to jute powder and kaolin when methylene blue there is promotion.
3 gained compound sewage inorganic agent of embodiment is to Cu2+The performance of absorption is as shown in figure 14, it can be seen that embodiment 3 produces
Object is to Cu2+Adsorbance be 270 mg/g.
Figure 15 is unmodified raw material to Cu2+The performance map of absorption, in conjunction with embodiment 3 in Figure 14 and embodiment 7 to Cu2+
Adsorbance, it can be deduced that conclusion, compound sewage inorganic agent to Cu2+Adsorbance be much larger than unmodified raw material absorption
Amount, and the compound sewage inorganic agent after kaolin is added to Cu2+Large amount of adsorption in be not added kaolin compound sewage processing
The adsorbance of agent.
3 gained compound sewage inorganic agent of embodiment is as shown in figure 16 to the performance of methylene blue adsorption number, it can be seen that implements
3 product of example is 123.3 mg/g to the adsorbance of methylene blue.
Figure 17 is performance map of the unmodified raw material to methylene blue adsorption number, right in conjunction with embodiment 3 in Figure 16 and embodiment 7
The adsorbance of methylene blue, it can be deduced that conclusion, compound sewage inorganic agent are much larger than unmodified sample to the adsorbance of methylene blue
The adsorbance of product, and the compound sewage inorganic agent after kaolin is added to the large amount of adsorption of methylene blue in kaolin is not added
The adsorbance of compound sewage inorganic agent.
Embodiment 4
By roundpod jute leaf bar powder (leaf powder and bar powder mass ratio be 1:1) 15 g, 7.5 g of kaolin, anionic polyacrylamide
(APAM) 9 g are put into the ball grinder of polytetrafluoroethylene (PTFE), alumina balls (by quality ratio, the big ball accounting 20% of 10 mm of diameter, straight
Ball accounting 50%, diameter 3mm bead accounting 30% in 5 mm of diameter) it with the mass ratio of compound material is 6:1, the revolving speed of ball mill is
500 rpm, 4 h of ball milling obtain mixed-powder after ball milling.Other processing methods are the same as embodiment 1.
Gained clay mineral/biomass combined sewage-treating agent Adsorption of Cu2+, methylene blue condition with embodiment 1.
Fig. 8 is roundpod jute leaf bar powder, kaolin, roundpod jute leaf bar powder/bentonite composite material sewage-treating agent XRD, compound
The XRD diagram of material sewage-treating agent substantially and it is kaolinic matches, but the intensity at peak, compared to lower, this is jute powder package
Reason.
Fig. 9 is roundpod jute leaf bar powder/kaolin composite material sewage-treating agent SEM figure, as can be seen from the figure kaolin
Surface wrapped up jute powder, the comparison that this structure illustrates that kaolin and jute powder combine is close, in compound sewage processing
Agent Adsorption of Cu2+Or its synergistic effect is played to jute powder and kaolin when methylene blue there is promotion.
4 gained compound sewage inorganic agent of embodiment is to Cu2+The performance of absorption is as shown in figure 14, it can be seen that embodiment 4 produces
Object is to Cu2+Adsorbance be 239.5 mg/g.
Figure 15 is unmodified raw material to Cu2+The performance map of absorption, in conjunction with embodiment 4 in Figure 14 and embodiment 7 to Cu2+
Adsorbance, it can be deduced that conclusion, compound sewage inorganic agent is to Cu2+Adsorbance be much larger than unmodified raw material adsorbance,
And the compound sewage inorganic agent after kaolin is added is to Cu2+Large amount of adsorption in kaolin compound sewage inorganic agent is not added
Adsorbance.
4 gained compound sewage inorganic agent of embodiment is as shown in figure 16 to the performance of methylene blue adsorption number, it can be seen that implements
4 product of example is 188.9 mg/g to the adsorbance of methylene blue.
Figure 17 is performance map of the unmodified raw material to methylene blue adsorption number, right in conjunction with embodiment 4 in Figure 16 and embodiment 7
The adsorbance of methylene blue, it can be deduced that conclusion, compound sewage inorganic agent are much larger than unmodified sample to the adsorbance of methylene blue
The adsorbance of product, and the compound sewage inorganic agent after kaolin is added to the large amount of adsorption of methylene blue in kaolin is not added
The adsorbance of compound sewage inorganic agent.
Embodiment 5
Jute powder (bar powder) 15 g, 1.5 g of concave convex rod, 3 g of anionic polyacrylamide (APAM) are put into polytetrafluoroethylene (PTFE)
In ball grinder, alumina balls (by quality ratio, the big ball accounting 20% of 10 mm of diameter, ball accounting 50%, diameter 3mm in 5 mm of diameter
Bead accounting 30%) it with the mass ratio of compound material is 6:1, the revolving speed of ball mill is 500 rpm, 4 h of ball milling, is obtained after ball milling
Mixed-powder.Other processing methods are the same as embodiment 1.
Gained clay mineral/biomass combined sewage-treating agent Adsorption of Cu2+, methylene blue condition with embodiment 1.
In the embodiment, jute powder is jute stalk powder, and polyacrylamide is anionic polyacrylamide (APAM).
Figure 10 is jute stalk powder, concave convex rod, jute powder/bumps rod composite material sewage-treating agent XRD, and composite material is dirty
The XRD diagram of water treatment agent matches with concave convex rod substantially, but the intensity at peak compare it is lower.
Figure 11 is jute powder/bumps rod composite material sewage-treating agent SEM figure, and as can be seen from the figure concave convex rod wraps up
In the outside of jute powder, the comparison that this structure illustrates that concave convex rod and jute powder combine is close, in compound sewage inorganic agent
Adsorption of Cu2+Or its synergistic effect is played to jute powder and concave convex rod when methylene blue there is promotion.
Figure 14 is compound sewage inorganic agent to Cu2+The performance map of absorption, as can be seen from the figure embodiment 5 is to Cu2+Suction
Attached amount is 246.8 mg/g.
Figure 15 is unmodified raw material to Cu2+The performance map of absorption, in conjunction with embodiment 5 in Figure 14 and embodiment 7 to Cu2+
Adsorbance, it can be deduced that conclusion, compound sewage inorganic agent is to Cu2+Adsorbance be much larger than unmodified raw material adsorbance,
And the compound sewage inorganic agent after concave convex rod is added is to Cu2+Large amount of adsorption in concave convex rod compound sewage inorganic agent is not added
Adsorbance.
5 gained sewage-treating agent of embodiment is as shown in figure 16 to the performance of methylene blue adsorption number, it can be seen that embodiment 5 produces
Object is 132.3 mg/g to the adsorbance of methylene blue.
Figure 17 is performance map of the unmodified raw material to methylene blue adsorption number, right in conjunction with embodiment 5 in Figure 16 and embodiment 7
The adsorbance of methylene blue, it can be deduced that conclusion, compound sewage inorganic agent are much larger than unmodified sample to the adsorbance of methylene blue
The adsorbance of product, and the compound sewage inorganic agent after concave convex rod is added to the large amount of adsorption of methylene blue in concave convex rod is not added
The adsorbance of compound sewage inorganic agent.
Embodiment 6
Jute powder (bar powder) 15 g, 1.5 g of concave convex rod, 9 g of polyacrylamide are put into the ball grinder of polytetrafluoroethylene (PTFE), aoxidized
Aluminium ball (by quality ratio, the big ball accounting 20% of 10 mm of diameter, ball accounting 50%, diameter 3mm bead accounting 30% in 5 mm of diameter)
It is 6:1 with the mass ratio of compound material, the revolving speed of ball mill is 500 rpm, 4 h of ball milling, obtains mixed-powder after ball milling.Other
Processing method is the same as embodiment 1.
Gained clay mineral/biomass combined sewage-treating agent Adsorption of Cu2+, methylene blue condition with embodiment 1.
In the embodiment, jute powder is jute stalk powder, and polyacrylamide is anionic polyacrylamide (APAM).
Figure 12 be jute powder, concave convex rod, jute powder/concave convex rod compound sewage inorganic agent XRD, compound sewage inorganic agent
XRD diagram matches with concave convex rod substantially, but the intensity at peak compare it is lower.
Figure 13 is jute stalk powder/concave convex rod compound sewage inorganic agent SEM figure, as can be seen from the figure the surface of concave convex rod
Jute powder is wrapped up, interlayer also has jute powder, and the comparison that this structure illustrates that concave convex rod and jute powder combine is close, multiple
Close sewage-treating agent Adsorption of Cu2+Or its synergistic effect is played to jute powder and concave convex rod when methylene blue there is promotion.
6 gained sewage-treating agent of embodiment is to Cu2+The performance of absorption is as shown in figure 14, it can be seen that 6 product pair of embodiment
Cu2+Adsorbance be 272.9 mg/g.
Figure 15 is unmodified raw material to Cu2+The performance map of absorption, in conjunction with embodiment 6 in Figure 14 and embodiment 7 to Cu2+
Adsorbance, it can be deduced that conclusion, compound sewage inorganic agent is to Cu2+Adsorbance be much larger than unmodified raw material adsorbance,
And the compound sewage inorganic agent after concave convex rod is added is to Cu2+Large amount of adsorption in concave convex rod compound sewage inorganic agent is not added
Adsorbance.
6 gained compound sewage inorganic agent of embodiment is as shown in figure 16 to the absorption property of methylene blue, it can be seen that implements
6 product of example is 157.3 mg/g to the adsorbance of methylene blue.
Figure 17 is unmodified raw material to methylene blue adsorption number performance map, in conjunction with 7 pairs of Asias of embodiment 6 in Figure 16 and embodiment
The adsorbance of methyl blue, it can be deduced that conclusion, compound sewage inorganic agent are much larger than unmodified sample to the adsorbance of methylene blue
Adsorbance, and the compound sewage inorganic agent being added after concave convex rod is multiple in concave convex rod is not added to the large amount of adsorption of methylene blue
Close the adsorbance of sewage-treating agent.
Embodiment 7
15 g of jute powder, 9 g of polyacrylamide are put into the ball grinder of polytetrafluoroethylene (PTFE), alumina balls are (by quality ratio, directly
Ball accounting 50%, diameter 3mm bead accounting 30% in the big ball accounting 20% of 10 mm of diameter, 5 mm of diameter) with the mass ratio of compound material
For 6:1, the revolving speed of ball mill is 500 rpm, 4 h of ball milling.Other processing methods are the same as embodiment 1.
Gained clay mineral/biomass combined sewage-treating agent Adsorption of Cu2+, methylene blue condition with embodiment 1.
In the embodiment, jute powder is roundpod jute leaf powder, and polyacrylamide is anionic polyacrylamide (APAM).
7 gained sewage-treating agent of embodiment is to Cu2+The performance of absorption is as shown in figure 14, it can be seen that 7 product pair of embodiment
Cu2+Adsorbance be 124.4 mg/g.
7 gained sewage-treating agent of embodiment is as shown in figure 16 to the performance of methylene blue adsorption number, it can be seen that embodiment 7 produces
Object is 106.3 mg/g to the adsorbance of methylene blue.
Claims (10)
1. a kind of clay mineral/agricultural abandoned biomass compound sewage inorganic agent preparation method, which is characterized in that including following
Step:
(1) using agricultural abandoned biomass, clay mineral, binder as raw material, by clay mineral, agricultural abandoned biomass, bonding
The mass ratio (1 ~ 5) of agent: 10:(2 ~ 6) ball milling；
(2) 40 ~ 95 DEG C of hot water are added in the resulting mixed powder of the step (1), be thoroughly mixed uniformly, hot water and mixed
The mass ratio for closing powder is (2.5 ~ 5): 1；
(3) by aging processing after the sealing of step (2) resulting material；
(4) mixed slurry mixing, tabletting, drying obtained by step (3)；
(5) compound sewage inorganic agent is made through broken, sieving in the resulting dry block of step (4).
2. clay mineral/agricultural abandoned biomass compound sewage inorganic agent preparation method according to claim 1, feature
Be, the agricultural abandoned biomass be jute stalk and one of leaf, stalk, corncob, bagasse, rice husk, pericarp, algae or
The mixture of two or more arbitrary proportions.
3. clay mineral/agricultural abandoned biomass compound sewage inorganic agent preparation method according to claim 1, feature
It is, the clay mineral is bentonite, kaolin, concave convex rod, sepiolite, montmorillonite, galapectite, vermiculite, smectite, slope
The mixture of one or more of thread stone, illite arbitrary proportion.
4. clay mineral/agricultural abandoned biomass compound sewage inorganic agent preparation method according to claim 1, feature
It is, the binder is starch, protein, animal glue, Sodium Alginate, sodium carboxymethylcellulose, polyacrylamide, polypropylene
One or more of sour sodium, polyvinyl pyridine salt, polyethyleneimine, polydimethyl diallyl ammonium chloride arbitrary proportion
Mixture.
5. clay mineral/agricultural abandoned biomass compound sewage inorganic agent preparation method according to claim 1, feature
It is, when ball milling, abrading-ball used was one or more, the abrading-ball of alumina balls, zirconia ball, mullite ball, stainless steel ball
With the mass ratio (3 ~ 6) of material: 1, abrading-ball grind diameter be 3 ~ 15 mm, rotational speed of ball-mill be 50 ~ 600 rpm, Ball-milling Time be 1 ~ 20
h。
6. clay mineral/agricultural abandoned biomass compound sewage inorganic agent preparation method according to claim 1, feature
It is, the aging condition is to keep the temperature 5 ~ 48 h in 40 ~ 100oC.
7. clay mineral/agricultural abandoned biomass compound sewage inorganic agent preparation method according to claim 1, feature
It is, the drying refers to that moisture content is in (2 ~ 10) % in 80 ~ 150 DEG C of dry 2 ~ 16 h；It is crushed in the step (5), mistake
After sieve, gained composite treating agent particle size range is 0.1 ~ 1 mm.
8. clay mineral made from any preparation method of claim 1 to 7/agricultural abandoned biomass compound sewage processing
Agent.
9. clay mineral according to any one of claims 8/agricultural abandoned biomass compound sewage inorganic agent heavy metal in absorption effluent
The application of ion.
10. clay mineral according to any one of claims 8/agricultural abandoned biomass compound sewage inorganic agent has engine dyeing in absorption effluent
The application of material.
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| CN111320303A (en) * | 2020-03-13 | 2020-06-23 | 广东东华园林绿化工程有限公司 | Purification treatment system and method for recycling sewage of water spraying pool |
| CN111921499A (en) * | 2020-09-07 | 2020-11-13 | 中国热带农业科学院海口实验站 | Ball-milling modified composite biochar and preparation method and application thereof |
| CN113860954A (en) * | 2021-11-03 | 2021-12-31 | 华东师范大学重庆研究院 | Blue algae sludge treatment method |
| CN114392732A (en) * | 2022-01-21 | 2022-04-26 | 北京师范大学 | Composite material based on clay mineral and preparation method thereof |
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| CN102614851A (en) * | 2012-04-09 | 2012-08-01 | 西北师范大学 | Preparation of palygorskite clay/plant stalk composite adsorbent and application of composite adsorbent in treating printing and dyeing wastewater |
| CN108689407A (en) * | 2018-06-26 | 2018-10-23 | 中国科学院生态环境研究中心 | A kind of technique that binder pressed active carbon is exempted from abandoned biomass preparation |
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| CN102614851A (en) * | 2012-04-09 | 2012-08-01 | 西北师范大学 | Preparation of palygorskite clay/plant stalk composite adsorbent and application of composite adsorbent in treating printing and dyeing wastewater |
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