CN104069822A - Microwave organic modified particle bentonite/attapulgite adsorbent and preparation method thereof - Google Patents
Microwave organic modified particle bentonite/attapulgite adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a microwave organic modified particle bentonite/attapulgite adsorbent and a preparation method thereof. The technical scheme is as follows: bentonite powder and attapulgite powder are used as main raw materials and mixed at the mass ratio of 1: (0.3-0.5); the bentonite powder and the attapulgite powder, and water are uniformly mixed at the mass ratio of 1: (1.2-2), dried at the temperature of 100-110 DEG C, smashed until the particle diameters are within 0.2-0.9 mm and calcined for 2-2.5 h at the temperature of 720-780 DEG C; under the microwave condition, the mixture is modified by the hexadecyl trimethyl ammonium bromide equivalent to 25-200% of calcined particle bentonite/attapulgite to obtain the microwave organic modified particle bentonite/attapulgite adsorbent. According to the invention, the microwave organic modified particle bentonite/attapulgite adsorbent is simple in technology, short in modified time, environment-friendly and low in energy consumption; prepared microwave organic modified particle bentonite/attapulgite adsorbent is great in particle diameter, good in adsorptive performance and suitable for the treatment of wastewater containing heavy metal irons and chlorophenol.
Description
Technical field
The invention belongs to adsorbent technical field.Relate in particular to the organically-modified particle bentonite/attapulgite of a kind of microwave adsorbent and preparation method thereof.
Background technology
Natural clay is cheap and easy to get and specific area is large, and inorganic, organic pollution are had to certain adsorption capacity.Bentonite is a class aboundresources, cheap stratiform natural minerals clay, unmodified front not strong to hydrophobic organic compound adsorption capacity.Because the basic structure of bentonite is two-layer Si-O tetrahedron therebetween one deck A1-O octahedron, wherein Si
4+, Al
3+can be by Mg
2+, Fe
2+, Li
+and Ni
2+at a low price ion replaces, thereby causes bentonite structure cell electricity price unsaturated, makes to be with between bentonite bed permanent negative electrical charge, and the hydrated cation that this negative electrical charge has an exchangeability by interlayer conventionally carrys out balance.Therefore, natural montmorillonite has good ion-exchange performance, utilize bentonitic this ion-exchange performance to bentonite surface, to carry out suitable modification according to the structural property of target contaminant, the bentonite after modification has higher absorption property to pollutant.Zhu etc. use the surfactant-modified bentonite surface with longer carbochain, experimental result shows that the organobentonite after modification obviously improves (L. Zhu to the adsorption capacity of organic pollution, X. Ruan, B. Chen, R. Zhu. Efficient removal and mechanisms of water soluble aromatic contaminants by a reduced-charge bentonite modified with benzyltrimethyl-ammonium cation. Chemosphere. 2008, 70:1987-1994), but their conventional modification method modification time used is long, consume energy high, filtered fluid can bring pollution problem.
Heating using microwave relies on the feature that its penetration capacity is stronger, make almost heating simultaneously of material inside and outside, and traditional heating mode is that material is from outward appearance to inner essence relied on to heat exchange pattern heating, so microwave is faster compared with traditional heating speed, has saved the heat time and has reduced heat leakage.Li Ji we study discovery, with the synthetic organobentonite of microwave, do not need to stir, the ion-exchange reactions time is short, the organobentonite under the same conditions clearance of acid scarlet in water being made compared with conventional method has improved 50.89%, reach 97.21% (Li Jiwu, Zhu Lizhong, Cai Wei is strong. organic performance in the synthetic organobentonite of microwave and adsorbed water thereof. and China Environmental Science. 2004, 24 (6): 665-669), but their microwave modification for be Powdered bentonite, because bentonite has swellability, with Powdered bentonite in treatment waste water, can bring the problem of secondary pollution, in addition, microwave still can produce filtrate later, when using concentrated surfactant modification, also need the surfactant of material surface to wash away, cleaning solution is also a kind of pollution sources.
Summary of the invention
The present invention is intended to overcome prior art defect, and object is to provide that a kind of technique is simple, modification time is short, energy consumption is low and the preparation method of the organically-modified particle bentonite/attapulgite of eco-friendly microwave adsorbent; The organically-modified particle bentonite/attapulgite of the microwave adsorbent particle diameter prepared by the method is large, free settling and absorption property good, be applicable to the processing containing heavy metal ion and chlorinated phenol waste water.
To achieve these goals, the preparation method of the technical solution used in the present invention is:
Step 1, to take bentonite powder and attapulgite powder be raw material, mixes, and obtains Powdered bentonite/attapulgite; In Powdered bentonite/attapulgite, add water again, mix, obtain clod shape bentonite/attapulgite; Then by described clod shape bentonite/attapulgite dry 16 ~ 24h under the condition of 100 ~ 110 ℃, make block bentonite/attapulgite.
Wherein: the mass ratio of bentonite powder ︰ attapulgite powder is 1 ︰ (0.3 ~ 0.5); The mass ratio of the protruding Bang Tu of Powdered bentonite/Ao ︰ water is 1 ︰ (1.2 ~ 2).
Step 2, described block bentonite/attapulgite is crushed to particle diameter is 0.2 ~ 0.9mm, obtain particle bentonite/attapulgite, again particle bentonite/attapulgite is calcined to 2 ~ 2.5h under the condition of 720 ~ 780 ℃, the particle bentonite/attapulgite after being calcined.
Step 3, under 50 ~ 80 ℃ of conditions, by softex kw, by 25 ~ 200%CEC(of the particle bentonite/attapulgite after calcining, be cation exchange capacity, lower same) be dissolved in 0.95 ~ 1L distilled water, obtain softex kw solution.
Step 4, pack the particle bentonite/attapulgite after calcining into gauze sack, again to add the ratio of the particle bentonite/attapulgite 100 ~ 106g after calcining in every liter of softex kw solution, in softex kw solution, add the particle bentonite/attapulgite after calcining, the mixed liquor of the particle bentonite/attapulgite after obtaining softex kw and calcining, then the mixed liquor of the particle bentonite/attapulgite after softex kw and calcining is placed in to micro-wave oven microwave 15 ~ 90min, make the organically-modified particle bentonite/attapulgite of microwave adsorbent.
The CEC of described bentonite powder is 90 ~ 110mmol/100g.
The power of described micro-wave oven is 500 ~ 5000W.
Owing to adopting technique scheme, the present invention compared with prior art has following good effect:
Particle bentonite has large particle diameter, free settling in water, but particle bentonite intensity is not high, and particle bentonite is poor to the adsorption effect of pollutant.The present invention adopts attapulgite to make binding agent, by high-temperature calcination, has increased the bentonitic intensity of particle, under microwave condition, particle bentonite is carried out to surface modification, shorten modification time, through the particle bentonite of surface modification, the adsorption capacity of the pollutant in waste water is improved.
The present invention is without follow-up suction filtration, oven dry in the process of preparing the organically-modified particle bentonite/attapulgite of microwave adsorbent, and more traditional method of modifying is compared and shortened modification time, therefore technique is simple; Simultaneously due to the pollution problem of having avoided filtrate to bring without filtrate, therefore environmental friendliness; Owing to having reduced energy consumption without oven dry.
The organically-modified particle bentonite/attapulgite of microwave adsorbent prepared by the present invention carries out modification to particle bentonite/attapulgite and obtains, compare with the adsorbent that existing method of modifying makes, granular materials particle diameter is large, and free settling in water is processed waste water and can not brought the problem of secondary pollution.
The present invention is in preparing the organically-modified particle bentonite/attapulgite of microwave adsorbent process, owing to wrapping up in by gauze bag attached bag, avoided surfactant due to excessive concentration in the accumulation of particle bentonite/attapulgite's surface, improved the adsorption effect of the organically-modified particle bentonite/attapulgite of microwave adsorbent.
The organically-modified particle bentonite/attapulgite of microwave adsorbent prepared by the present invention is compared with particle bentonite/attapulgite adsorbent, particle bentonite/attapulgite adsorbent of preparing through microwave modification disperses more, increased the specific area of adsorbent, thereby more adsorption site can be provided, finally improve the adsorption effect of adsorbent to target contaminant.
Therefore, technique of the present invention is simple, modification time is short, environmental friendliness and energy consumption low; The particle diameter of the organically-modified particle bentonite/attapulgite of prepared microwave adsorbent is large, free settling and absorption property good, be applicable to the processing containing heavy metal ion and chlorinated phenol waste water.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the particle bentonite/attapulgite after a kind of calcining of step 1 ~ bis-preparation of the present invention;
Fig. 2 is through the SEM figure of the organically-modified particle bentonite/attapulgite of the microwave adsorbent of step 3 ~ tetra-preparation shown in Fig. 1;
Fig. 3 is the FTIR figure of the particle bentonite/attapulgite after the calcining shown in the organically-modified particle bentonite/attapulgite adsorbent of the microwave shown in Fig. 2 and Fig. 1;
Fig. 4 be particle bentonite/attapulgite after the calcining shown in the organically-modified particle bentonite/attapulgite adsorbent of the microwave shown in Fig. 2 and Fig. 1 X-diffraction pattern.
The specific embodiment
Below in conjunction with the specific embodiment and accompanying drawing, the invention will be further described, not the restriction to its protection domain:
In this specific embodiment: the CEC(of described bentonite powder is cation exchange capacity, lower same) be 90 ~ 110mmol/100g, in embodiment, repeat no more.
embodiment 1
The organically-modified particle bentonite/attapulgite of a kind of microwave adsorbent and preparation method thereof.Its concrete steps are:
Step 1, to take bentonite powder and attapulgite powder be raw material, mixes, and obtains Powdered bentonite/attapulgite; In Powdered bentonite/attapulgite, add water again, mix, obtain clod shape bentonite/attapulgite; Then by described clod shape bentonite/attapulgite dry 16 ~ 18h under the condition of 100 ~ 110 ℃, make block bentonite/attapulgite.
Wherein: the mass ratio of bentonite powder ︰ attapulgite powder is 1 ︰ (0.3 ~ 0.4); The mass ratio of the protruding Bang Tu of Powdered bentonite/Ao ︰ water is 1 ︰ (1.2 ~ 1.4).
Step 2, described block bentonite/attapulgite is crushed to particle diameter is 0.2 ~ 0.45mm, obtain particle bentonite/attapulgite, again particle bentonite/attapulgite is calcined to 2 ~ 2.5h under the condition of 720 ~ 780 ℃, the particle bentonite/attapulgite after being calcined.
Step 3, under 50 ~ 80 ℃ of conditions, the 25 ~ 50%CEC of particle bentonite/attapulgite by softex kw after by calcining is dissolved in 0.95 ~ 1L distilled water, obtains softex kw solution.
Step 4, pack the particle bentonite/attapulgite after calcining into gauze sack, again to add the ratio of the particle bentonite/attapulgite 100 ~ 102g after calcining in every liter of softex kw solution, in softex kw solution, add the particle bentonite/attapulgite after calcining, the mixed liquor of the particle bentonite/attapulgite after obtaining softex kw and calcining, then the mixed liquor of the particle bentonite/attapulgite after softex kw and calcining is placed in to micro-wave oven microwave 70 ~ 90min that power is 500 ~ 1000W, make the organically-modified particle bentonite/attapulgite of microwave adsorbent.
With the organically-modified particle bentonite/attapulgite of the prepared microwave of the present embodiment adsorbent, to concentration, be 30mg/L 2,4-Dichlorophenol solution carries out adsorption treatment, at the organically-modified particle bentonite/attapulgite of described microwave adsorbent dosage, be under the speed of agitator of 2g/L, 260r/min and condition that adsorption time is 120min, the clearance of 2,4-Dichlorophenol is 80.8 ~ 95.4%.
embodiment 2
The organically-modified particle bentonite/attapulgite of a kind of microwave adsorbent and preparation method thereof.Its concrete steps are:
Step 1, to take bentonite powder and attapulgite powder be raw material, mixes, and obtains Powdered bentonite/attapulgite; In Powdered bentonite/attapulgite, add water again, mix, obtain clod shape bentonite/attapulgite; Then by described clod shape bentonite/attapulgite dry 18 ~ 20h under the condition of 100 ~ 110 ℃, make block bentonite/attapulgite.
Wherein: the mass ratio of bentonite powder ︰ attapulgite powder is 1 ︰ (0.4 ~ 0.5); The mass ratio of the protruding Bang Tu of Powdered bentonite/Ao ︰ water is 1 ︰ (1.4 ~ 1.6).
Step 2, described block bentonite/attapulgite is crushed to particle diameter is 0.45 ~ 0.9mm, obtain particle bentonite/attapulgite, again particle bentonite/attapulgite is calcined to 2 ~ 2.5h under the condition of 720 ~ 780 ℃, the particle bentonite/attapulgite after being calcined.
Step 3, under 50 ~ 80 ℃ of conditions, the 50 ~ 100%CEC of particle bentonite/attapulgite by softex kw after by calcining is dissolved in 0.95 ~ 1L distilled water, obtains softex kw solution.
Step 4, pack the particle bentonite/attapulgite after calcining into gauze sack, again to add the ratio of the particle bentonite/attapulgite 102 ~ 104g after calcining in every liter of softex kw solution, in softex kw solution, add the particle bentonite/attapulgite after calcining, the mixed liquor of the particle bentonite/attapulgite after obtaining softex kw and calcining, then the mixed liquor of the particle bentonite/attapulgite after softex kw and calcining is placed in to micro-wave oven microwave 50 ~ 70min that power is 1000 ~ 2000W, make the organically-modified particle bentonite/attapulgite of microwave adsorbent.
The Cd that is 10mg/L to concentration with the organically-modified particle bentonite/attapulgite of the prepared microwave of the present embodiment adsorbent
2+solution carries out adsorption treatment, at the organically-modified particle bentonite/attapulgite of described microwave adsorbent dosage, is under the speed of agitator of 2g/L, 260r/min and condition that adsorption time is 120min, Cd
2+clearance be 86.3 ~ 93.4%.
embodiment 3
The organically-modified particle bentonite/attapulgite of a kind of microwave adsorbent and preparation method thereof.Its concrete steps are:
Step 1, to take bentonite powder and attapulgite powder be raw material, mixes, and obtains Powdered bentonite/attapulgite; In Powdered bentonite/attapulgite, add water again, mix, obtain clod shape bentonite/attapulgite; Then by described clod shape bentonite/attapulgite dry 20 ~ 22h under the condition of 100 ~ 110 ℃, make block bentonite/attapulgite.
Wherein: the mass ratio of bentonite powder ︰ attapulgite powder is 1 ︰ (0.3 ~ 0.4); The mass ratio of the protruding Bang Tu of Powdered bentonite/Ao ︰ water is 1 ︰ (1.8 ~ 2).
Step 2, described block bentonite/attapulgite is crushed to particle diameter is 0.45 ~ 0.9mm, obtain particle bentonite/attapulgite, again particle bentonite/attapulgite is calcined to 2 ~ 2.5h under the condition of 720 ~ 780 ℃, the particle bentonite/attapulgite after being calcined.
Step 3, under 50 ~ 80 ℃ of conditions, the 100 ~ 150%CEC of particle bentonite/attapulgite by softex kw after by calcining is dissolved in 0.95 ~ 1L distilled water, obtains softex kw solution.
Step 4, pack the particle bentonite/attapulgite after calcining into gauze sack, again to add the ratio of the particle bentonite/attapulgite 104 ~ 106g after calcining in every liter of softex kw solution, in softex kw solution, add the particle bentonite/attapulgite after calcining, the mixed liquor of the particle bentonite/attapulgite after obtaining softex kw and calcining, then the mixed liquor of the particle bentonite/attapulgite after softex kw and calcining is placed in to micro-wave oven microwave 30 ~ 50min that power is 2000 ~ 3000W, make the organically-modified particle bentonite/attapulgite of microwave adsorbent.
The Pb that is 20mg/L to concentration with the organically-modified particle bentonite/attapulgite of the prepared microwave of the present embodiment adsorbent
2+solution carries out adsorption treatment, at the organically-modified particle bentonite/attapulgite of described microwave adsorbent dosage, is under the speed of agitator of 2g/L, 260r/min and condition that adsorption time is 120min, Pb
2+clearance is 86.3 ~ 90.1%.
embodiment 4
The organically-modified particle bentonite/attapulgite of a kind of microwave adsorbent and preparation method thereof.Its concrete steps are:
Step 1, to take bentonite powder and attapulgite powder be raw material, mixes, and obtains Powdered bentonite/attapulgite; In Powdered bentonite/attapulgite, add water again, mix, obtain clod shape bentonite/attapulgite; Then by described clod shape bentonite/attapulgite dry 22 ~ 24h under the condition of 100 ~ 110 ℃, make block bentonite/attapulgite.
Wherein: the mass ratio of bentonite powder ︰ attapulgite powder is 1 ︰ (0.3 ~ 0.4); The mass ratio of the protruding Bang Tu of Powdered bentonite/Ao ︰ water is 1 ︰ (1.6 ~ 1.8).
Step 2, described block bentonite/attapulgite is crushed to particle diameter is 0.45 ~ 0.9mm, obtain particle bentonite/attapulgite, again particle bentonite/attapulgite is calcined to 2 ~ 2.5h under the condition of 720 ~ 780 ℃, the particle bentonite/attapulgite after being calcined.
Step 3, under 50 ~ 80 ℃ of conditions, the 150 ~ 200%CEC of particle bentonite/attapulgite by softex kw after by calcining is dissolved in 0.95 ~ 1L distilled water, obtains softex kw solution.
Step 4, pack the particle bentonite/attapulgite after calcining into gauze sack, again to add the ratio of the particle bentonite/attapulgite 100 ~ 102g after calcining in every liter of softex kw solution, in softex kw solution, add the particle bentonite/attapulgite after calcining, the mixed liquor of the particle bentonite/attapulgite after obtaining softex kw and calcining, then the mixed liquor of the particle bentonite/attapulgite after softex kw and calcining is placed in to micro-wave oven microwave 15 ~ 30min that power is 3000 ~ 5000W, make the organically-modified particle bentonite/attapulgite of microwave adsorbent.
The Cr that is 20mg/L to concentration with the organically-modified particle bentonite/attapulgite of the prepared microwave of the present embodiment adsorbent
6+solution carries out adsorption treatment, at the organically-modified particle bentonite/attapulgite of described microwave adsorbent dosage, is under the speed of agitator of 2g/L, 260r/min and condition that adsorption time is 120min, Cr
6+clearance is 63.1 ~ 70.5%.
This specific embodiment compared with prior art has following good effect:
Particle bentonite has large particle diameter, free settling in water, but particle bentonite intensity is not high, and particle bentonite is poor to the adsorption effect of pollutant.This specific embodiment adopts attapulgite to make binding agent, by high-temperature calcination, increased the bentonitic intensity of particle, under microwave condition, particle bentonite is carried out to surface modification, shorten modification time, through the particle bentonite of surface modification, the adsorption capacity of the pollutant in waste water is improved.
This specific embodiment is without follow-up suction filtration, oven dry in the process of preparing the organically-modified particle bentonite/attapulgite of microwave adsorbent, and more traditional method of modifying is compared and shortened modification time, therefore technique is simple; Simultaneously due to the pollution problem of having avoided filtrate to bring without filtrate, therefore environmental friendliness; Owing to having reduced energy consumption without oven dry.
The organically-modified particle bentonite/attapulgite of microwave adsorbent prepared by this specific embodiment carries out modification to particle bentonite/attapulgite and obtains, compare with the adsorbent that existing method of modifying makes, granular materials particle diameter is large, free settling in water, processes waste water and can not bring the problem of secondary pollution.
This specific embodiment is in preparing the organically-modified particle bentonite/attapulgite of microwave adsorbent process, owing to wrapping up in by gauze bag attached bag, avoided surfactant due to excessive concentration in the accumulation of particle bentonite/attapulgite's surface, improved the adsorption effect of the organically-modified particle bentonite/attapulgite of microwave adsorbent.
The organically-modified particle bentonite/attapulgite of microwave adsorbent prepared by this specific embodiment is compared with particle bentonite/attapulgite adsorbent, particle bentonite/attapulgite adsorbent of preparing through microwave modification disperses more, increased the specific area of adsorbent, thereby more adsorption site can be provided, finally improve the adsorption effect of adsorbent to target contaminant.
Fig. 1 is the SEM figure of the particle bentonite/attapulgite after a kind of calcining of step 1 ~ bis-preparation in embodiment 1, as seen from Figure 1: the bentonite before modification is sheet.Fig. 2 is through the SEM figure of the organically-modified particle bentonite/attapulgite of the microwave adsorbent of step 3 ~ tetra-preparation, as seen from Figure 2: the bentonite lamella after modification diminishes, and the dispersion more distributing shown in Fig. 1.Fig. 3 is the FTIR figure of the particle bentonite/attapulgite after the calcining shown in the organically-modified particle bentonite/attapulgite adsorbent of the microwave shown in Fig. 2 and Fig. 1, as seen from Figure 3: 2920cm after modification
-1c-H antisymmetric stretching vibration absworption peak and 2851cm
-1c-H flexural vibrations absworption peak obviously strengthen, this explanation modifier hexadecane level trimethylammonium bromide enters between bentonite bed.Fig. 4 be particle bentonite/attapulgite after the calcining shown in the organically-modified particle bentonite/attapulgite adsorbent of the microwave shown in Fig. 2 and Fig. 1 X-diffraction pattern, by Fig. 4, can be found out: the organically-modified particle bentonite/attapulgite of prepared microwave adsorbent is compared with particle bentonite/attapulgite, its angle of diffraction is offset to low angle, interlamellar spacing increases, through softex kw and ion-exchange occurs between bentonite bed, softex kw enters between bentonite bed in explanation.
Therefore, this specific embodiment technique is simple, modification time is short, environmental friendliness and energy consumption low; The particle diameter of the organically-modified particle bentonite/attapulgite of prepared microwave adsorbent is large, free settling and absorption property good, be applicable to the processing containing heavy metal ion and chlorinated phenol waste water.
Claims (4)
1. a preparation method for the organically-modified particle bentonite/attapulgite of microwave adsorbent, is characterized in that described preparation method is:
Step 1, to take bentonite powder and attapulgite powder be raw material, mixes, and obtains Powdered bentonite/attapulgite; In Powdered bentonite/attapulgite, add water again, mix, obtain clod shape bentonite/attapulgite; Then by described clod shape bentonite/attapulgite dry 16 ~ 24h under the condition of 100 ~ 110 ℃, make block bentonite/attapulgite;
Wherein: the mass ratio of bentonite powder ︰ attapulgite powder is 1 ︰ (0.3 ~ 0.5); The mass ratio of the protruding Bang Tu of Powdered bentonite/Ao ︰ water is 1 ︰ (1.2 ~ 2);
Step 2, described block bentonite/attapulgite is crushed to particle diameter is 0.2 ~ 0.9mm, obtain particle bentonite/attapulgite, again particle bentonite/attapulgite is calcined to 2 ~ 2.5h under the condition of 720 ~ 780 ℃, the particle bentonite/attapulgite after being calcined;
Step 3, under 50 ~ 80 ℃ of conditions, the 25 ~ 200%CEC of particle bentonite/attapulgite by softex kw after by calcining is dissolved in 0.95 ~ 1L distilled water, obtains softex kw solution;
Step 4, by calcining after particle bentonite/attapulgite pack gauze sack into, again to add the ratio of the particle bentonite/attapulgite 100 ~ 106g after calcining in every liter of softex kw solution, in softex kw solution, add the particle bentonite/attapulgite after calcining, the mixed liquor of the particle bentonite/attapulgite after obtaining softex kw and calcining; Then the mixed liquor of the particle bentonite/attapulgite after softex kw and calcining is placed in to micro-wave oven microwave 15 ~ 90min, makes the organically-modified particle bentonite/attapulgite of microwave adsorbent.
2. the preparation method of the organically-modified particle bentonite/attapulgite of microwave adsorbent according to claim 1, its feature is 90 ~ 110mmol/100g at the CEC of described bentonite powder.
3. the preparation method of the organically-modified particle bentonite/attapulgite of microwave adsorbent according to claim 1, its feature is 500 ~ 5000W at the power of described micro-wave oven.
4. the organically-modified particle bentonite/attapulgite of a microwave adsorbent, is characterized in that the organically-modified particle bentonite/attapulgite of described microwave adsorbent is according to the prepared organically-modified particle bentonite/attapulgite of the microwave adsorbent of preparation method of the organically-modified particle bentonite/attapulgite of microwave adsorbent described in any one in claim 1 ~ 3.
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| CN106311173A (en) * | 2016-09-21 | 2017-01-11 | 安徽瀚景观规划设计院有限公司 | Preparation method of water pollution absorption material |
| CN106925240A (en) * | 2017-04-12 | 2017-07-07 | 明光市国星凹土有限公司 | A kind of organic modified particles attapulgite clay adsorbent and preparation method thereof |
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| CN110368895A (en) * | 2019-08-14 | 2019-10-25 | 上海理工大学 | Modified attapulgite-bentonite high efficiency composition clay filler preparation method and application |
| CN110980755A (en) * | 2019-12-31 | 2020-04-10 | 湖北三鼎科技有限公司 | Preparation method of high-expansion-times sodium bentonite |
| CN110980755B (en) * | 2019-12-31 | 2023-04-21 | 湖北三鼎科技有限公司 | Preparation method of high-expansion sodium-base bentonite |
| CN111701578A (en) * | 2020-06-30 | 2020-09-25 | 广西夏阳环保科技有限公司 | Adsorbent for sewage treatment and preparation method thereof |
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