CN103272560B - Novel composite water treatment material and preparation method thereof - Google Patents
Novel composite water treatment material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a novel composite water treatment material and a preparation method thereof. The novel composite water treatment material contains tourmaline, sepiolite and graphene oxide or graphene. According to the preparation method, the graphene or the graphene oxide is wrapped on the surfaces of the sepiolite and the tourmaline by a reflux method, so the adsorptive property of the sepiolite on organic wastewater can be effectively improved by utilizing the large surface area of the graphene or the graphene oxide. The novel composite material has the characteristics of high adsorption efficiency, small using amount, energy conservation and the like, in particular, the sepiolite and the tourmaline are almost not consumed, so the treatment cost can be greatly reduced, and the dangerousness that dye molecules belonging to organic matters difficult to degrade are immersed into natural water and accumulated in the environment is avoided. Meanwhile, the graphene oxide and the graphene have good antibacterial property, so the phenomenon that activated sludge is increased too fast can be effectively improved, and considerable economic benefit, environmental benefit and social benefit are achieved.
Description
Technical field
The present invention relates to a kind of novel compound material for water treatment, is exactly a kind of formula, preparation method and application of the compound material for water treatment containing tourmaline, sepiolite and graphene oxide or Graphene specifically.
Background technology
Along with world population is increased sharply and economic developing rapidly; city size constantly expands; the demand of water resource and the discharge capacity of industrial wastewater rapidly, make the world especially water resources in china be faced with huge crisis, using water wisely, to reduce sewage discharge row extremely urgent.But, industrial wastewater discharge severe overweight, especially dyeing waste water at present.The dyeing waste water of textile printing and dyeing industry discharge is one of major polluting sources in China's industrial system, and according to State Environmental Protection Administration's statistics, the dyeing waste water total amount of dyeing discharge is positioned at five of total flow controls of national each industrial department discharge.2004,13.6 hundred million cubes of whole industry displacement, its gross contamination emission (in COD) is positioned at six of each Ministry of Industry family status.Dyeing waste water belongs to the organic wastewater that contains a certain amount of recalcitrant substance.Its pollutant levels high (COD), colourity is dark, is one of unmanageable industrial wastewater.
At present, printing-dyeing waste water treatment process complexity, need to combine several method conventionally.Conventional method has two classes at present: one is physico-chemical process: in sewage, add adsorbent to remove the pollutant in sewage.But these class methods because dosing expense is high, remove pollutant not thoroughly, sludge quantity is large and be difficult to further processing, can produce certain secondary pollution, generally do not use separately, only as the auxiliary process of biochemical treatment; Another kind is biochemical process: utilize the effect of microorganism, make organic matter degradation in sewage, be adsorbed and a kind of processing method of removing.But in dyeing waste water, contain a large amount of bio-refractory dyestuffs, and in these dyestuffs, there are the groups such as a large amount of phenyl ring, amido, azo, therefore biochemical method is not satisfactory to the treatment effect of printing and dyeing water.Therefore, cheap, efficient material for water treatment is favourably welcome.
Sorbing material is to utilize the porous of solid matter to make one or more materials in waste water be attracted to the surface of solids or method inner and that remove.The research and development of novel absorption material are significant to energy-saving and emission-reduction and protection of the environment.
Patent CN1431042A (2003) provides the processing method of a kind of fly ash absorbent and waste water.The raw material of this adsorbent is flyash, a kind of industrial residue.Flyash has cellular structure, and chemical composition is complicated, is improved through peracid modification and heat modification specific area, dyeing waste water is had to good treatment effect, cheap economic environmental protection, but adsorption capacity is not very large comparatively speaking, and not reproducible utilization.
Patent CN101143312A (2008) provides a kind of manufacture and renovation process of graininess mud adsorbent.This adsorbent, taking waste red mud and flyash as main raw material(s), adds adhesive, exciting agent and pore former and makes through roasting.To good sewage processing effect, and renewable, can recycled for multiple times.But manufacturing process is loaded down with trivial details, and need high temperature roast, cost is higher.
Patent CN102531226A (2012) provides a kind of method of processing acid dyes printing and dyeing water, simply summarizes its step and is exactly: first adjust pH, then aeration decolouring, finally reduces the COD in water with the sepiolite of solid-carried catalyst.The method has that technique is simple, floor space is little, colourity to sour fuel dyeing waste water and COD obvious processing effect etc. feature.But the preparation method of sepiolite solid-carried catalyst is loaded down with trivial details, and need the high-temperature activation of long period, preparation cost is higher.
Patent CN2611008Y provides a kind of sepiolite filtering membrane type filter, sepiolite filter membrane in this equipment is making beating after adding water in container with sepiolite fibre, wood-fibred, glass fibre, resin glue, filter skeleton is all inserted in filter pulp, copies and be plated on gauze with paper technology.This filter membrane can be widely used in drinking water, grape wine, beverage, white wine and edible wet goods industry.But this filter membrane is when for the treatment of industrial wastewater, and flow velocity is slower, and efficiency is lower.
Graphene is made up of monolayer carbon atom, has cellular two dimensional crystal structure, is current known thin material in the world.Graphene has higher specific area (2600m
2/ g), under outstanding heat conductivility (3500W/mK) and ultimate strength (1100GPa), room temperature, possess electron mobility (15000cm at a high speed
2v
-1k
-1), also there is antibacterial action simultaneously, obtain broad research and application in fields such as nanometer instrument, composite, hydrogen storage materials.
Graphene oxide is the lamellar compound of a kind of interlamellar spacing of obtaining through degree of depth liquid phase oxidation of flake graphite much larger than former graphite, after peeling off, can form monolithic layer structure (being graphene oxide), be the important growth of Graphene, graphene oxide has the features such as the large and ion-exchange capacity of specific area is strong.Many oxy radicals are introduced through snperoxiaized graphite in its sheet surfaces, as hydrophilic active groups such as hydroxyl, carboxyl, epoxy radicals, thereby make it be easy in polar solvent, form stable single sheet, make graphene oxide can with most metals and the compound composite that obtains excellent performance of metal oxide.
Cost graphene preparation method minimum and that the most easily accomplish scale production is graphene oxide reducing process at present.HUMMERS method and prepare the general method of graphene oxide, graphene oxide reducing process is that crystalline flake graphite is reacted and generates graphene oxide with strong acid and strong oxidation material, be prepared into graphene oxide (mono-layer graphite oxide alkene) through ultrasonic dispersion, add reducing agent to remove the oxy radical on graphite oxide surface, as carboxyl, epoxy radicals and hydroxyl, obtain Graphene.Graphene oxide reducing process making Graphene cost is lower and efficient, environmental protection, and can large-scale industrial production.
Summary of the invention
The invention provides a kind of high efficiency composition material for water treatment, in this material, contain tourmaline, sepiolite and graphene oxide or Graphene, wherein tourmaline has self power generation polarity, the effectively organic matter in degrading waste water, tourmaline can also be releasing far infrared simultaneously, can effectively improve the rate of adsorption of this material to organic matter and ion; Sepiolite has relatively large specific area, organic matter and yin, yang ion in can quick adsorption waste water; Graphite oxide specific area is large, and contain-the OH ,-oxygen-containing functional groups such as COOH, has hydrophily, can effectively remove the pollutant in water, and Graphene does not contain functional group, water insoluble, but the easy organic compound such as hydro carbons, aromatic hydrocarbons in adsorbed water.The present invention makes a kind of high efficiency composition material for water treatment with this raw material, and preparation method is simple, with low cost, and good to the treatment effect of sewage, consumption is little, environmental protection.
Technical scheme of the present invention is:
A kind of compound material for water treatment, its composition and proportioning comprise:
The preparation method of described compound material for water treatment, is one of following two kinds of methods, comprises the following steps:
Method one: take graphene oxide, add the mixed solution of water and ethanol, ultrasonic dispersion obtains graphene oxide suspension, its proportioning is that the mixed solution of every 20～80ml adds 1.5～15g graphene oxide, the graphene oxide suspension obtaining is added in reactor, add again sepiolite fibre and tourmaline powder through peracid modification, its proportioning is that every 1.5～15g graphene oxide adds sepiolite fibre and the 0.05～40g tourmaline powder of 10～49.95g through peracid modification, add again the mixed solution of water and ethanol, wherein, the every 50g of quality sum of sepiolite and tourmaline need to add the mixed solution of 400-600ml water and ethanol, by reactor heating reflux reaction 3 hours, obtain the coated sepiolite of graphene oxide in surface and the mixed liquor of tourmaline, by mixed liquor suction filtration, dry, grind, obtain compound material for water treatment (being called for short T/GO/S),
Or, method two: take graphene oxide, add the mixed solution of water and ethanol, ultrasonic dispersion obtains graphene oxide suspension, its proportioning is that the mixed solution of every 20～80ml adds 1.5～15g graphene oxide, pour the suspension obtaining into reactor, add again sepiolite fibre and tourmaline powder through peracid modification, its proportioning is that every 1.5～15g graphene oxide adds sepiolite fibre and the 0.05～40g tourmaline powder of 10～49.95g through peracid modification, add again the mixed solution of water and ethanol, wherein, the every 50g of quality sum of sepiolite and tourmaline need to add the mixed solution of 400-600ml water and ethanol, by reactor heating reflux reaction 3 hours, then in reactor, add hydrazine hydrate according to the ratio of every 1～4g graphene oxide interpolation 1～2g hydrazine hydrate, react 30 minutes, the graphene oxide of reduced powder surface, then reactant is taken out, suction filtration, dry, grinding, obtain compound material for water treatment (being called for short T/G/S)
The preparation method of described compound material for water treatment, also comprises the forming step of composite: get the compound material for water treatment making above, then add water glass binder, stir, then add in mould, after shaping, take out, under 80 DEG C～300 DEG C conditions, dry; Its proportioning is that the compound material for water treatment of every 20g adds 1～2ml water glass binder.
Water in described method one or method two and the mixed solution of ethanol, composition is volume ratio water: ethanol=1:3～3:1.
Compared with prior art, advantage of the present invention is:
The selected tourmaline of the present invention has releasing far infrared function, can activate the especially organic molecule in dyeing waste water of organic wastewater, accelerates the movement velocity of molecule, thereby improves the rate of adsorption; Tourmaline also has absorption property, can effectively adsorb organic matter and various ion in waste water; The simultaneously also spontaneous polarity of tool of tourmaline, the organic matter in can degrading waste water; Tourmaline is also had a surface-active, hydrone can be resolved into hydroxyl ion and improve the dissolved oxygen in water.
The selected sepiolite of the present invention is a kind of fibrous moisture rich magnesium silicate mineral, and theoretical specific area can reach 900m
2/ g, wherein inner ratio surface area 500m
2/ g, external surface area 400m
2/ g, so large specific area and loose structure is the immediate cause that sepiolite has stronger adsorption capacity.But the adsorptivity of natural sea afrodite and ion exchangeable are very weak, so reaching far away theoretical value, its specific area need to carry out modification.After acid modification, the duct area in sepiolite fibre and volume increase, and duct number increases, and specific area significantly increases, the adsorption capacity of organic matter and various ions is obviously strengthened, and cheap.
Graphene or graphene oxide material that the present invention uses have the advantages that specific area is large, can improve 5～10 times with the rate of adsorption and the adsorption capacity of the compound rear sepiolite of sepiolite; After compound with tourmaline, the rate of adsorption and the adsorption capacity that can improve tourmaline can improve 3～10 times.Graphene oxide and Graphene also have antibacterial action, use graphene oxide or Graphene to process the growth and breeding that waste water can suppress bacterium in waste water.
The present invention can directly be used as filtrate, for the treatment of sanitary sewage, industrial wastewater, environment accident etc., has especially solved that in the processing procedure of dyeing waste water, cost is high, decolouring is difficult, COD removes the problems such as difficult, can simplify the treatment process of dyeing waste water.Have cheap, can reuse, the feature of efficient, energy-conservation, environmental protection.
The present invention adopts circumfluence method that Graphene or graphene oxide are wrapped in to sepiolite and tourmaline powder surface, prepare a kind of advanced composite material (ACM), this material physical properties is stable, function admirable, cheap, and there is absolute predominance compared with traditional sorbing material.
The present invention has chosen 4 groups of compound material for water treatment and has carried out contrast test with sepiolite and active carbon after sour modified active, find that four groups of compound material for water treatment are generally improved to the treatment effeciency of organic wastewater, be respectively 86.6%, 80.3%, 95.3%, 90.4%, and sepiolite and active carbon are only 30.4% and 2.3% to the treatment effeciency of simulation dyeing waste water.Compared with other sorbing materials, efficiency of the present invention is high, energy-conservation, floor space is little, especially the sepiolite in the present invention and tourmaline are consumed hardly, therefore can greatly reduce processing cost, the danger of having avoided belonging to the dye molecule immersion natural water body of hardly degraded organic substance and accumulate in environment, has considerable economic benefit, environmental benefit and social benefit.
Detailed description of the invention
The preparation of graphene oxide described in the present invention adopts improved hummers method, preparation method can be with reference to Wei Gao, people's document Engineered Graphite Oxide Materials for Application in Water Purification such as Mainak Majumder, ACS Appl.Mater.Interfaces2011,3,1821 – 1826.
The preparation method of the sepiolite fibre through peracid modification the present invention relates to is: the beaker that first takes 500g and crossed the sepiolite raw ore of 20 mesh sieves and be placed in 5000ml, add 3112ml deionized water, 388ml mass fraction is 36% hydrochloric acid solution, with the rotating speed high speed dispersion 1h of 1500r/min; Then by repeated multiple times above-mentioned slurries filtering and washing, until pH is neutral; Finally above-mentioned filter cake is dried under 80 DEG C of conditions, grinding is weighed, and finally obtains the sepiolite fibre through peracid modification.
Embodiment mono-
1. take 15.00g graphene oxide, add the water of 80mL1:1 and the mixed solution of ethanol, ultrasonic 20min left and right, obtain finely dispersed graphene oxide suspension, add in round-bottomed flask, (m) (particle diameter 0.3～30 μ m), puts into round-bottomed flask to particle diameter 100～200 μ, then adds water and the alcohol mixed solution that 520mL volume ratio is 1:1 in flask with 0.05g tourmaline powder to take respectively sepiolite fibre after 49.95g acid modification;
2. flask is put into electric heating cover heating while condensing reflux 3 hours, graphene oxide is wrapped on sepiolite fibre and tourmaline powder, suction filtration, dry, grinding, obtain the compound material for water treatment of tourmaline/graphene oxide/sepiolite (being called for short T/GO/S).
3. to adding 20 glass glues that drip in the compound material for water treatment of the 20g making (T/GO/S), stir, add in mould, after moulding, take out, under 100 DEG C of conditions, dry, obtain the T/GO/S of moulding.
Embodiment bis-
1. take 1.50g graphene oxide, add the water of 20mL1:1 and the mixed solution of ethanol, ultrasonic 20min left and right, obtain finely dispersed graphene oxide suspension, add in round-bottomed flask, take respectively sepiolite fibre and 0.05g tourmaline powder after 49.95g acid modification, put into round-bottomed flask, then add water and the alcohol mixed solution that 320mL volume ratio is 1:1 in flask;
Step 2～3 are with embodiment mono-.
Embodiment tri-
1. take 15.00g graphene oxide, add the water of 80mL1:1 and the mixed solution of ethanol, ultrasonic 20min left and right, obtain finely dispersed graphene oxide suspension, add in round-bottomed flask, take respectively sepiolite fibre and 40.00g tourmaline powder after 10.00g acid modification, put into round-bottomed flask, then add water and the alcohol mixed solution that 520mL volume ratio is 1:1 in flask;
Step 2～3 are with embodiment mono-.
Embodiment tetra-
1. take 1.50g graphene oxide, add the water of 20mL1:1 and the mixed solution of ethanol, ultrasonic 20min left and right, obtain finely dispersed graphene oxide suspension, add in round-bottomed flask, take respectively sepiolite fibre and 40.00g tourmaline powder after 10.00g acid modification, put into round-bottomed flask, then add water and the alcohol mixed solution that 320mL volume ratio is 1:1 in flask;
Step 2～3 are with embodiment mono-.
Embodiment five
1. take 15.00g graphene oxide, add the water of 80mL1:1 and the mixed solution of ethanol, ultrasonic 20min left and right, obtain finely dispersed graphene oxide suspension, add in round-bottomed flask, take respectively sepiolite fibre and 0.05g tourmaline powder after 49.95g acid modification, put into round-bottomed flask, then add water and the alcohol mixed solution that 520mL volume ratio is 1:1 in flask;
2. flask is put into electric heating cover heating while condensing reflux 3 hours, graphene oxide is wrapped on sepiolite fibre and tourmaline powder, in flask, add afterwards 30g hydrazine hydrate reaction 30 minutes, the graphene oxide of reduced powder surface, then reactant is taken out, suction filtration, dry, grinding, obtain the compound material for water treatment of tourmaline/Graphene/sepiolite (being called for short T/G/S).
3. to adding 20 glass glues that drip in the 20gT/G/S making, stir, add in mould, after moulding, take out, under 100 DEG C of conditions, dry, obtain the T/G/S of moulding.
Embodiment six
1. take 1.50g graphene oxide, add the water of 20mL1:1 and the mixed solution of ethanol, ultrasonic 20min left and right, obtain finely dispersed graphene oxide suspension, add in round-bottomed flask, take respectively sepiolite fibre and 0.05g tourmaline powder after 49.95g acid modification, put into round-bottomed flask, then add water and the alcohol mixed solution that 320mL volume ratio is 1:1 in flask;
2. flask is put into electric heating cover heating while condensing reflux 3 hours, graphene oxide is wrapped on sepiolite fibre and tourmaline powder, in flask, add afterwards 0.375g hydrazine hydrate reaction 30 minutes, the graphene oxide of reduced powder surface, then reactant is taken out, suction filtration, dry, grinding, obtain the compound material for water treatment of tourmaline/Graphene/sepiolite (being called for short T/G/S).
Step 3 is with embodiment five.
Embodiment seven
1. take 15.00g graphene oxide, add the water of 80mL1:1 and the mixed solution of ethanol, ultrasonic 20min left and right, obtain finely dispersed graphene oxide suspension, add in round-bottomed flask, take respectively sepiolite fibre and 40.00g tourmaline powder after 10.00g acid modification, put into round-bottomed flask, then add water and the alcohol mixed solution that 520mL volume ratio is 1:1 in flask;
Step 2～3 are with embodiment five.
Embodiment eight
1. take 1.50g graphene oxide, add the water of 20mL1:1 and the mixed solution of ethanol, ultrasonic 20min left and right, obtain finely dispersed graphene oxide suspension, add in round-bottomed flask, take respectively sepiolite fibre and 40.00g tourmaline powder after 10.00g acid modification, put into round-bottomed flask, then add water and the alcohol mixed solution that 320mL volume ratio is 1:1 in flask;
Step 2～3 are with embodiment six.
Contrast test
Choose 4 groups of compound material for water treatment and common heat radiation coating and carry out contrast test, prepare the compound material for water treatment of tourmaline/graphene oxide/sepiolite according to the step of embodiment mono-, be labeled as " 1# "; Prepare the compound material for water treatment of tourmaline/Graphene/sepiolite according to the step of embodiment five, be labeled as " 2# "; Prepare the compound material for water treatment of tourmaline/graphene oxide/sepiolite according to the step of embodiment tetra-, be labeled as " 3# "; Prepare the compound material for water treatment of tourmaline/Graphene/sepiolite according to the step of embodiment eight, be labeled as " 4# "; Step according to the sour modification of sepiolite is prepared sepiolite fibre, is labeled as " S "; Active carbon is labeled as " AC ".Utilize visible spectrophotometer to test and assess respectively above-mentioned material to simulating the treatment effect of dyeing waste water.Experimental procedure is as follows:
1. get the simulation dyeing waste water (methylene blue solution) of six parts of 100mL4mg/L
2. take respectively #1, #2, #3, #4, S and the AC of equivalent, join in simulation dyeing waste water simultaneously, survey its light absorption value every 20min with visible spectrophotometer, and calculate its clearance, as table 1.
Table 1, four kinds of composites and sepiolite, the treatment effeciency of active carbon to simulation dyeing waste water
Sepiolite after sour modification, to the adsorption efficiency of simulation dyeing waste water far away higher than active carbon, is almost 10 times of active carbon as can be seen from Table 1; And the adsorption efficiency of four kinds of composites has far away higher than sepiolite, be almost 3 times of sepiolite, be 30 times of active carbon.
As can be seen here, the present invention adopts circumfluence method that Graphene or graphene oxide are wrapped in to sepiolite and tourmaline surface, utilize the surface area that Graphene or graphene oxide are larger, can effectively improve the absorption property of sepiolite to organic wastewater, the rate of adsorption of four kinds of Compound Water treatment effeciencies obviously improves, in the time of 20min, the treatment effeciency of simulation dyeing waste water has been reached to 98.8%, 85.4%, 96.5%, 84.2%, and sepiolite and active carbon are only 30.4% and 2.3% to the treatment effeciency of simulation dyeing waste water.Compared with other sorbing materials, it is high that advanced composite material (ACM) provided by the invention has adsorption efficiency, consumption is few, the feature such as energy-conservation, especially sepiolite and tourmaline are consumed hardly, therefore can greatly reduce processing cost, the danger of having avoided belonging to the dye molecule immersion natural water body of hardly degraded organic substance and accumulate in environment, simultaneous oxidation Graphene and Graphene have good anti-microbial property, if the activated sludge process by this composite in wastewater treatment process is combined, can effectively improve activated sludge and increase too fast problem, there is considerable economic benefit, environmental benefit and social benefit.
Claims (3)
1. a compound material for water treatment, is characterized by this compound material for water treatment and is prepared by following methods and obtain, and preparation method is one of following two kinds of methods, comprises the following steps:
Method one: take graphene oxide, add the mixed solution of water and ethanol, ultrasonic dispersion obtains graphene oxide suspension, its proportioning is that the mixed solution of every 20～80ml adds 1.5～15g graphene oxide, the graphene oxide suspension obtaining is added in reactor, add again sepiolite fibre and tourmaline powder through peracid modification, its proportioning is that every 1.5～15g graphene oxide adds sepiolite fibre and the 0.05～40g tourmaline powder of 10～49.95g through peracid modification, add again the mixed solution of water and ethanol, wherein, the every 50g of quality sum of sepiolite and tourmaline need to add the mixed solution of 400-600ml water and ethanol, by reactor heating reflux reaction 3 hours, obtain the coated sepiolite of graphene oxide in surface and the mixed liquor of tourmaline, by mixed liquor suction filtration, dry, grind, obtain compound material for water treatment,
Or, method two: take graphene oxide, add the mixed solution of water and ethanol, ultrasonic dispersion obtains graphene oxide suspension, its proportioning is that the mixed solution of every 20～80ml adds 1.5～15g graphene oxide, pour the suspension obtaining into reactor, add again sepiolite fibre and tourmaline powder through peracid modification, its proportioning is that every 1.5～15g graphene oxide adds sepiolite fibre and the 0.05～40g tourmaline powder of 10～49.95g through peracid modification, add again the mixed solution of water and ethanol, wherein, the every 50g of quality sum of sepiolite and tourmaline need to add the mixed solution of 400-600ml water and ethanol, by reactor heating reflux reaction 3 hours, then in reactor, add hydrazine hydrate according to the ratio of every 1～4g graphene oxide interpolation 1～2g hydrazine hydrate, react 30 minutes, the graphene oxide of reduced powder surface, then reactant is taken out, suction filtration, dry, grinding, obtain compound material for water treatment.
2. compound material for water treatment as claimed in claim 1, is characterized by the forming step that also comprises composite: get the compound material for water treatment making above, then add water glass binder, stir, then add in mould, after shaping, take out, under ° C condition of 80 ° of C～300, dry; Its proportioning is that the compound material for water treatment of every 20g adds 1～2ml water glass binder.
3. compound material for water treatment as claimed in claim 1, the water in method one or method two described in it is characterized by and the mixed solution of ethanol, composition is volume ratio water: ethanol=1:3～3:1.
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| CN103990436B (en) * | 2014-06-11 | 2016-08-10 | 河北工业大学 | Tourmaline/scion grafting modification sulfur-bearing redox graphene composite adsorbing material and preparation method thereof |
| CN104001475B (en) * | 2014-06-11 | 2016-02-17 | 河北工业大学 | Tourmaline/scion grafting modification sulfur-bearing Graphene composite adsorbing material and preparation method thereof |
| CN103990435B (en) * | 2014-06-11 | 2016-06-08 | 河北工业大学 | A kind of tourmaline/scion grafting modification sulfur-bearing graphene oxide composite adsorbing material and preparation method thereof |
| JP7117117B2 (en) * | 2018-03-14 | 2022-08-12 | オルガノ株式会社 | Water treatment agent, method for producing water treatment agent, and water treatment method |
| CN108970258B (en) * | 2018-07-13 | 2021-03-12 | 深圳市喀尔木环保材料有限公司 | Preparation method of air purifier filter element |
| CN108905968B (en) * | 2018-07-18 | 2021-10-15 | 山东利特纳米技术有限公司 | Preparation method of graphene oxide composite filter element material and water purification filter element |
| CN110523394B (en) * | 2019-09-02 | 2021-09-21 | 山东利特纳米技术有限公司 | Graphene oxide-PADA (polycyclic aromatic hydrocarbon) molding material as well as preparation method and application thereof |
| CN110918010B (en) * | 2019-12-06 | 2022-02-01 | 石家庄铁道大学 | Preparation method of sepiolite-graphene composite aerogel |
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