CN111001393A - Sodium alginate-based loaded nano-red titanium manganese ore/brown coal-based active coke hydrogel and preparation method thereof - Google Patents
Sodium alginate-based loaded nano-red titanium manganese ore/brown coal-based active coke hydrogel and preparation method thereof Download PDFInfo
- Publication number
- CN111001393A CN111001393A CN201911354045.8A CN201911354045A CN111001393A CN 111001393 A CN111001393 A CN 111001393A CN 201911354045 A CN201911354045 A CN 201911354045A CN 111001393 A CN111001393 A CN 111001393A
- Authority
- CN
- China
- Prior art keywords
- hydrogel
- sodium alginate
- active coke
- preparing
- based active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 107
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 71
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 71
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 71
- 239000003077 lignite Substances 0.000 title claims abstract description 62
- 239000000571 coke Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 46
- 229910052748 manganese Inorganic materials 0.000 claims description 46
- 239000011572 manganese Substances 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 43
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 26
- 230000002572 peristaltic effect Effects 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 16
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 16
- 239000012498 ultrapure water Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000004005 microsphere Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 10
- 230000008929 regeneration Effects 0.000 abstract description 9
- 238000011069 regeneration method Methods 0.000 abstract description 9
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 238000001782 photodegradation Methods 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 17
- 239000001110 calcium chloride Substances 0.000 description 14
- 229910001628 calcium chloride Inorganic materials 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 229940099607 manganese chloride Drugs 0.000 description 4
- 235000002867 manganese chloride Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- IXZOTKANSDQAHZ-UHFFFAOYSA-N manganese(ii) titanate Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Mn+2] IXZOTKANSDQAHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000011504 laterite Substances 0.000 description 1
- 229910001710 laterite Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- 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
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
-
- 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
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- 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
Abstract
The invention belongs to the field of adsorption-photodegradation water treatment, and discloses a sodium alginate-based loaded nano-red titanium manganese ore/brown coal-based active coke hydrogel and a preparation method thereof. According to the invention, the loaded nano manganese titanate/brown coal-based active coke powder is prepared into hydrogel by utilizing the cross-linking effect of sodium alginate, and hydrophilic and hydrophobic refractory organic pollutants can be removed simultaneously by utilizing the surface characteristics of the hydrogel; the preparation process is simple and easy to implement, the prepared hydrogel can control the granularity and is convenient to recover from a liquid phase, the quality of effluent is improved, and the use cost is low; the in-situ regeneration can be realized rapidly, and the repeated use stability is good; no toxicity and no secondary pollution to environment.
Description
Technical Field
The invention belongs to the technical field of adsorption and purification, and particularly relates to sodium alginate-based loaded nano-red titanium manganese ore/brown coal-based active coke hydrogel and a preparation method thereof.
Background
With the development of social urbanization and industrialization, a large amount of untreated sewage and wastewater in cities are discharged into city landscape water bodies such as rivers, reservoirs and the like, so that the phenomena of eutrophication, odor, blackening and the like are easy to occur, and the natural ecological restoration capability of the cities is damaged to different degrees. In particular, in many production processes in the industries of mining and metallurgy, mechanical manufacturing, chemical industry, electronics, instruments and the like, a large amount of industrial wastewater is generated, which contains many harmful substances that are difficult to biodegrade, causing the harmful substances to exist in the natural environment for a long time, and being continuously enriched in organisms through food chains and the like, which brings serious harm to the natural environment and human health.
Among the existing wastewater treatment methods, the adsorption method is widely adopted due to the advantages of simple equipment, wide application range, good treatment effect and the like. The key technology of the adsorption method is the selection of the adsorbent, however, most of the existing adsorbents are powder, are difficult to separate from water after being adsorbed and saturated, are easy to cause secondary pollution and cannot be regenerated. The development of cheap, high-performance and renewable environment-friendly adsorbents by combining the modern chemical modification technology and the material composite technology is the development direction of research.
The brown coal-based active coke has the advantages of good adsorption and catalytic properties, easily obtained preparation raw materials, stable chemical properties and the like, and has practical significance in the technical field of environmental water and gas pollution treatment by replacing active carbon with the active coke. However, although the lignite-based activated coke has a good adsorption function and is low in cost, the adsorption capacity of the lignite-based activated coke is limited, the lignite-based activated coke needs to be replaced when the adsorption is saturated, frequent replacement causes high cost, and the effect of continuous purification and remediation is difficult to achieve.
Due to the special material structure of the manganese hureaulite, the manganese hureaulite has visible light regeneration characteristics. According to the visible light regeneration characteristic of the manganese hureaulite, the manganese hureaulite is mainly applied to photocatalytic reaction in the prior art. At present, no report related to the preparation of a renewable adsorbent by combining manganese laterite, brown coal-based active coke and sodium alginate is found.
Disclosure of Invention
Aiming at the defects of the adsorbent in the prior art, the invention aims to provide a preparation method of sodium alginate-based loaded nano-red titanium manganese ore/brown coal-based active coke hydrogel. The invention creatively utilizes the combination of the biomass-based material and the manganese ruthenate/brown coal-based active coke, and the hydrogel prepared under the action of the peristaltic pump not only has high porosity, large specific surface area and strong adsorption capacity, but also has the renewable function.
The invention also aims to provide the sodium alginate-based nano-red titanium manganese ore/brown coal-based active coke hydrogel prepared by the preparation method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of sodium alginate-based loaded nano-red titanium manganese ore/brown coal-based active coke powder hydrogel comprises the following steps:
s1, preparing a sodium alginate solution: taking a proper amount of sodium alginate powder, adding a certain amount of ultrapure water into the sodium alginate powder, and continuously stirring for 10-20 min to obtain a sodium alginate solution with the concentration of 2-5 wt%;
s2, preparing a mixed solution: adding the manganese ruthenate/lignite-based active coke powder into the sodium alginate solution obtained in the step S1 to obtain a mixed solution, then adding ultrapure water, and uniformly stirring to obtain the sodium alginate solution;
s3, preparing hydrogel: dripping the mixed solution obtained in the step S2 into a calcium chloride solution by using a peristaltic pump, fully crosslinking, stopping the peristaltic pump, and continuously stirring for a period of time to obtain hydrogel;
s4, hydrogel post-treatment: and (5) filtering out the hydrogel obtained in the step S3, repeatedly washing the hydrogel for 3-5 times by using deionized water, and then drying the hydrogel.
Since the sodium alginate powder is easily aggregated and the solution is viscous, it cannot be stirred by a magnetic stirrer, and in order to obtain a uniform sodium alginate aqueous solution, a continuous stirring treatment is performed by an egg beater in step S1.
Further, in step S2, the mass ratio of the sodium alginate solution to the manganese ruthenate/lignite-based active coke powder is 1-4: 1.
further, the concentration of the manganese ruthenate/lignite-based active coke in the mixed solution is 1-2 wt%.
Further, in step S3, the concentration of the calcium chloride solution is 1-3 wt%.
Further, in step S3, the flow rate of the peristaltic pump is 0.1-0.5 mL/min, and the continuous stirring time is 12-24 h.
Further, in step S4, the drying method is freeze drying or air drying.
Further, the freeze drying comprises the following specific steps: and (3) rapidly freezing the hydrogel by using liquid nitrogen, and then placing the frozen microspheres in a freeze dryer for freeze drying for 20-24 hours to obtain the hydrogel. The method adopts the liquid nitrogen to rapidly freeze the microspheres, so that the microspheres can be effectively prevented from being damaged in the slow crystallization process of water; freeze-drying the frozen microspheres in a freeze dryer to obtain microspheres with larger cavity sizes.
Further, the air-blast drying comprises the following specific steps: and (3) drying the microspheres in a blast drying oven at the temperature of 60-70 ℃ for 20-24 hours to obtain the hydrogel completely dehydrated.
A sodium alginate-based nano-red titanium manganese ore/brown coal-based active coke hydrogel loaded by the preparation method of the hydrogel.
The hydrogel prepared by the method can float on water, is easier to separate from water compared with powder, can control the granularity to facilitate the recovery from a liquid phase, improves the quality of effluent water, and has low use cost.
Compared with the prior art, the invention has the beneficial effects that:
the invention creatively utilizes the combination of the biomass-based material and the manganese ruthenate/brown coal-based active coke, adopts the peristaltic pump to directly prepare the materials into microspheres to obtain the sodium alginate-based manganese ruthenate/brown coal-based active coke hydrogel, and has simple preparation process and convenient operation; the method utilizes the cross-linking effect of sodium alginate to prepare the loaded nano manganese titanate/brown coal-based active coke powder into hydrogel, and can remove hydrophilic and hydrophobic refractory organic pollutants simultaneously by utilizing the surface characteristics of the hydrogel.
The hydrogel obtained by the invention has the regeneration capacity of the manganese ruthenate and the adsorption capacity of the lignite-based active coke, and the addition of sodium alginate has a synergistic effect, so that the adsorption capacity of the hydrogel is effectively improved, in-situ rapid regeneration can be realized under visible light, the hydrogel is good in repeated use stability and non-toxic, and secondary pollution of nano manganese titanate to the environment is effectively avoided.
The hydrogel can realize the cyclic regeneration of the adsorption material by utilizing visible light, does not need to frequently replace the adsorbent, achieves the good effect of continuous purification and repair, particularly has the adsorption-photodegradation effect on substances which are difficult to biodegrade, and can fill the technical blank of the regeneration of the adsorbent.
Drawings
FIG. 1 is an infrared spectrum diagram of sodium alginate-based loaded nano-red titanium manganese ore/brown coal-based active coke hydrogel prepared by the invention.
FIG. 2 is an infrared spectroscopic analysis of nano-sized manganese ruthenate ore of the present invention.
FIG. 3 is an infrared spectrum analysis diagram of sodium alginate provided by the present invention.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following specific examples.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
The embodiment provides a preparation method of sodium alginate-based loaded nano-red titanium manganese ore/lignite-based active coke hydrogel, which comprises the following steps:
s1, preparing a sodium alginate solution: taking a proper amount of sodium alginate powder, preparing with ultrapure water to obtain a sodium alginate solution with the concentration of 2wt%, and continuously stirring the solution for 10min by using an egg beater in the preparation process to obtain a uniform sodium alginate solution for later use;
s2, preparing a mixed solution: adding the manganese ruthenate/brown coal-based active coke powder into the sodium alginate solution obtained in the step S1 to obtain a mixed solution, wherein the mass ratio of the sodium alginate solution to the manganese ruthenate/brown coal-based active coke powder is 4:1, then adding ultrapure water, and uniformly stirring to obtain the sodium alginate solution; wherein the concentration of the manganese roseite/brown coal-based active coke in the mixed solution is 2 wt%;
s3, preparing hydrogel
S31, preparing a calcium chloride solution: taking a proper amount of calcium chloride, preparing a 3wt% calcium chloride aqueous solution by using ultrapure water, and fully dissolving and uniformly mixing for later use;
s32, preparing hydrogel: dripping the mixed solution obtained in the step S2 into the calcium chloride solution prepared in the step S31 by using a peristaltic pump, wherein the flow rate of the peristaltic pump is 0.1mL/min, fully crosslinking, stopping the peristaltic pump, and continuously stirring for 15 hours to obtain hydrogel;
s4, hydrogel post-treatment: and (4) filtering out the hydrogel belonging to the step S3, repeatedly washing the hydrogel for 3-5 times by using deionized water until the residual calcium chloride solution is sufficiently removed, then quickly freezing the microspheres by using liquid nitrogen, and then freeze-drying the frozen hydrogel in a freeze dryer for 24 hours to obtain the hydrogel with larger cavity size.
The preparation method of the manganese ruthenate/lignite-based active coke in the embodiment is as follows:
adding 0.01mol of manganese chloride into a mixed solution containing 0.2mol of distilled water and 0.2mol of ethanol, adjusting the pH value of a reaction system to be 2 by adopting hydrochloric acid, continuously stirring, and reacting for 30min at 75 ℃;
secondly, adding 0.002mol of hexadecyl trimethyl ammonium bromide into the reaction system, adding an ethanol solution until manganese chloride is completely dissolved, dropwise adding 0.01mol of tetraisopropyl titanate, continuously stirring, reacting for 12 hours at the temperature of 75 ℃, and then evaporating to obtain titanium dioxide-manganese oxide xerogel;
thirdly, drying the titanium dioxide-manganese oxide xerogel at 100 ℃ for 12h, grinding the dried titanium dioxide-manganese oxide xerogel into powder, and calcining the powder at 900 ℃ for 4h to obtain the manganese ruthenide powder;
and step four, dissolving 5g of the manganese ruthenate obtained in the step three in deionized water, wherein the concentration of the solution is 0.5%, immersing the manganese ruthenate into 15g of brown coal-based active coke, carrying out vacuum impregnation treatment for 4h at the vacuum degree of 0.001mbar, drying the manganese ruthenate/brown coal-based active coke for 5h at the temperature of 100 ℃, and finally firing the manganese ruthenate/brown coal-based active coke for 5h at the temperature of 300 ℃ to obtain the manganese ruthenate/brown coal-based active coke.
Example 2
The embodiment provides a preparation method of sodium alginate-based loaded nano-red titanium manganese ore/lignite-based active coke hydrogel, which comprises the following steps:
s1, preparing a sodium alginate solution: taking a proper amount of sodium alginate powder, preparing with ultrapure water to obtain a sodium alginate solution with the concentration of 5wt%, and continuously stirring the solution for 20min by using an egg beater in the preparation process to obtain a uniform sodium alginate solution for later use;
s2, preparing a mixed solution: adding the manganese ruthenate/brown coal-based active coke powder into the sodium alginate solution obtained in the step S1 to obtain a mixed solution, wherein the mass ratio of the sodium alginate solution to the manganese ruthenate/brown coal-based active coke powder is 3:1, then adding ultrapure water, and uniformly stirring to obtain the sodium alginate solution; wherein the concentration of the manganese roseite/brown coal-based active coke in the mixed solution is 1 wt%;
s3, preparing hydrogel
S31, preparing a calcium chloride solution: taking a proper amount of calcium chloride, preparing the calcium chloride into a 2wt% calcium chloride aqueous solution by using ultrapure water, and fully dissolving and uniformly mixing the calcium chloride aqueous solution for later use;
s32, preparing hydrogel: dripping the mixed solution obtained in the step S2 into the calcium chloride solution prepared in the step S31 by using a peristaltic pump, wherein the flow rate of the peristaltic pump is 0.3mL/min, fully crosslinking, stopping the peristaltic pump, and continuously stirring for 20 hours to obtain hydrogel;
s4, hydrogel post-treatment: and (4) filtering out the hydrogel belonging to the step S3, repeatedly washing the hydrogel for 3-5 times by using deionized water until the residual calcium chloride solution is sufficiently removed, then quickly freezing the microspheres by using liquid nitrogen, and then freeze-drying the frozen hydrogel in a freeze dryer for 24 hours to obtain the hydrogel with larger cavity size.
The preparation method of the manganese ruthenate/lignite-based activated coke in this example refers to example 1.
Example 3
The embodiment provides a preparation method of sodium alginate-based loaded nano-red titanium manganese ore/lignite-based active coke hydrogel, which comprises the following steps:
s1, preparing a sodium alginate solution: taking a proper amount of sodium alginate powder, preparing with ultrapure water to obtain a sodium alginate solution with the concentration of 2.5 wt%, and continuously stirring the solution for 15min by using an egg beater in the preparation process to obtain a uniform sodium alginate solution for later use;
s2, preparing a mixed solution: adding the manganese ruthenate/brown coal-based active coke powder into the sodium alginate solution obtained in the step S1 to obtain a mixed solution, wherein the mass ratio of the sodium alginate solution to the manganese ruthenate/brown coal-based active coke powder is 2:1, then adding ultrapure water, and uniformly stirring to obtain the sodium alginate solution; wherein the concentration of the manganese roseite/brown coal-based active coke in the mixed solution is 1.25 wt%;
s3, preparing hydrogel
S31, preparing a calcium chloride solution: taking a proper amount of calcium chloride, preparing the calcium chloride into a 1 wt% calcium chloride aqueous solution by using ultrapure water, and fully dissolving and uniformly mixing the calcium chloride aqueous solution for later use;
s32, preparing hydrogel: dripping the mixed solution obtained in the step S2 into the calcium chloride solution prepared in the step S31 by using a peristaltic pump, wherein the flow rate of the peristaltic pump is 0.4mL/min, fully crosslinking, stopping the peristaltic pump, and continuously stirring for 24 hours to obtain hydrogel;
s4, hydrogel post-treatment: and (4) filtering out the hydrogel in the step S3, repeatedly washing the hydrogel for 3-5 times by using deionized water until the residual calcium chloride solution is sufficiently removed, then placing the hydrogel in a blast drying oven, and drying the hydrogel for 24 hours at 70 ℃ until the water in the hydrogel is completely removed, thus obtaining the hydrogel.
The preparation method of the manganese ruthenate/lignite-based active coke in the embodiment is as follows:
adding 0.01mol of manganese chloride into a mixed solution containing 0.2mol of distilled water and 0.2mol of ethanol, adjusting the pH value of a reaction system to be 2 by adopting hydrochloric acid, continuously stirring, and reacting for 30min at 75 ℃;
secondly, adding 0.002mol of hexadecyl trimethyl ammonium bromide into the reaction system, adding an ethanol solution until manganese chloride is completely dissolved, dropwise adding 0.01mol of tetraisopropyl titanate, then adding 0.03mol of brown coal-based active coke according to a proportion, and reacting for 12 hours at the temperature of 75 ℃;
and thirdly, drying the obtained mixture at 100 ℃ for 12 hours, and calcining the dried mixture at 800 ℃ for 6 hours to obtain the brown coal-based active coke of the manganese ruthenate.
Example 4
The embodiment provides a preparation method of sodium alginate-based loaded nano-red titanium manganese ore/lignite-based active coke hydrogel, which comprises the following steps:
s1, preparing a sodium alginate solution: taking a proper amount of sodium alginate powder, preparing with ultrapure water to obtain a sodium alginate solution with the concentration of 4 wt%, and continuously stirring the solution for 18min by using an egg beater in the preparation process to obtain a uniform sodium alginate solution for later use;
s2, preparing a mixed solution: adding the manganese ruthenate/brown coal-based active coke powder into the sodium alginate solution obtained in the step S1 to obtain a mixed solution, wherein the mass ratio of the sodium alginate solution to the manganese ruthenate/brown coal-based active coke powder is 1:1, then adding ultrapure water, and uniformly stirring to obtain the sodium alginate solution; wherein the concentration of the manganese roseite/brown coal-based active coke in the mixed solution is 1.5 wt%;
s3, preparing hydrogel
S31, preparing a calcium chloride solution: taking a proper amount of calcium chloride, preparing the calcium chloride into a 1.5 wt% calcium chloride aqueous solution by using ultrapure water, and fully dissolving and uniformly mixing the calcium chloride aqueous solution for later use;
s32, preparing hydrogel: dripping the mixed solution obtained in the step S2 into the calcium chloride solution prepared in the step S31 by using a peristaltic pump, wherein the flow rate of the peristaltic pump is 0.2mL/min, fully crosslinking, stopping the peristaltic pump, and continuously stirring for 22 hours to obtain hydrogel;
s4, hydrogel post-treatment: and (4) filtering out the hydrogel in the step S3, repeatedly washing the hydrogel for 3-5 times by using deionized water until the residual calcium chloride solution is sufficiently removed, then placing the hydrogel in a blast drying oven, and drying the hydrogel for 24 hours at 70 ℃ until the water in the hydrogel is completely removed, thus obtaining the hydrogel.
The preparation method of the manganese ruthenate/lignite-based active coke in this example refers to example 3.
Comparative example 1
The comparative example provides a preparation method of sodium alginate-based loaded nano-red titanium manganese ore/brown coal-based active coke hydrogel, which is mainly different from the preparation method in example 3 in that: in step S1, a magnetic stirrer is used for stirring.
The preparation method of the manganese ruthenate/lignite-based active coke in the present comparative example refers to example 3.
Comparative example 2
The comparative example provides a preparation method of sodium alginate-based loaded nano-red titanium manganese ore/brown coal-based active coke hydrogel, which is mainly different from the preparation method in example 3 in that: in step S3, the stirring was not continued after the peristaltic pump was stopped.
The preparation method of the manganese ruthenate/lignite-based active coke in the present comparative example refers to example 3.
The hydrogel, the manganese ruthenate and the sodium alginate prepared by the method are subjected to infrared spectrum analysis, and specific results are shown in the figure 1-3.
Comparing fig. 1 with fig. 2-3, it can be seen that hydrogen bond association stretching vibration peaks exist in the hydrogel, and the hydrogel has the infrared characteristics of sodium alginate and manganese ruthenate. The hydrogen bond can increase the adsorption capacity of the hydrogel to hydrophilic pollutants, and the organic matters remained on the lignite-based active coke can increase the adsorption to hydrophobic compounds, so that the hydrogel has a smaller specific surface area than the nano manganese titanate, but has a better adsorption effect.
The hydrogel prepared by adopting the lignite-based active coke can increase the adsorption effect on hydrophilic and hydrophobic compounds, so that the concentration of pollutants around the manganese ruthenate is relatively increased, the degradation of the pollutants can be accelerated, the preparation of the nano manganese ruthenate plays an important role in the degradation effect, and the preparation of the hydrogel is related to the degradation rate of the pollutants.
The hydrogel prepared in examples 1 to 4 and comparative examples 1 to 2 was subjected to performance tests such as specific surface area, pore size, total pore volume and the like, and specific test results are shown in table 1.
TABLE 1
The hydrogel prepared by the method can float on water, and is easier to separate from water compared with powder; the loaded nano manganese titanate/brown coal-based active coke powder is prepared into hydrogel by utilizing the cross-linking effect of sodium alginate, and hydrophilic and hydrophobic refractory organic pollutants can be removed simultaneously by utilizing the surface characteristics of the hydrogel; the preparation process is simple and easy to implement, the prepared hydrogel can control the granularity and is convenient to recover from a liquid phase, the quality of effluent is improved, and the use cost is low. In addition, the hydrogel obtained by the invention has the regeneration capacity of the manganese ruthenate and the adsorption capacity of the lignite-based active coke, and the addition of sodium alginate has a synergistic effect, so that the adsorption capacity of the hydrogel is effectively improved, in-situ rapid regeneration can be realized under visible light, the hydrogel is good in repeated use stability and non-toxic, and secondary pollution of nano manganese titanate to the environment can be effectively avoided.
It should be understood that the above examples are only for clearly illustrating the technical solutions of the present invention, and are not intended to limit the embodiments of the present invention. It will be apparent to those skilled in the art that other variations and modifications can be made based on the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of sodium alginate-based loaded nano-red titanium manganese ore/lignite-based active coke hydrogel is characterized by comprising the following steps:
s1, preparing a sodium alginate solution: taking a proper amount of sodium alginate powder, adding a certain amount of ultrapure water into the sodium alginate powder, and continuously stirring for 10-20 min to obtain a sodium alginate solution with the concentration of 2-5 wt%;
s2, preparing a mixed solution: adding the manganese ruthenate/lignite-based active coke powder into the sodium alginate solution obtained in the step S1 to obtain a mixed solution, then adding ultrapure water, and uniformly stirring to obtain the sodium alginate solution;
s3, preparing hydrogel: dripping the mixed solution obtained in the step S2 into a calcium chloride solution by using a peristaltic pump, fully crosslinking, stopping the peristaltic pump, and continuously stirring for a period of time to obtain hydrogel;
s4, hydrogel post-treatment: and (5) filtering out the hydrogel obtained in the step S3, repeatedly washing the hydrogel for 3-5 times by using deionized water, and then drying the hydrogel.
2. The method for preparing the hydrogel according to claim 1, wherein the continuous stirring treatment is performed by using an egg beater in step S1.
3. The preparation method of the hydrogel according to claim 1, wherein in step S2, the mass ratio of the sodium alginate solution to the manganese ruthenate/lignite-based active coke powder is 1-4: 1.
4. the method for preparing the hydrogel according to claim 1, wherein in step S2, the concentration of the manganese ruthenate/lignite-based active coke in the mixed solution is 1-2 wt%.
5. The method for preparing the hydrogel according to claim 1, wherein the concentration of the calcium chloride solution in step S3 is 1 to 3 wt%.
6. The method for preparing the hydrogel according to claim 1, wherein in step S3, the flow rate of the peristaltic pump is 0.1 to 0.5mL/min, and the stirring time is 12 to 24 hours.
7. The method for producing a hydrogel according to claim 1, wherein the drying treatment is freeze drying or air drying in step S4.
8. The method for preparing the hydrogel according to claim 7, wherein the freeze-drying comprises the following steps: and (3) rapidly freezing the hydrogel by using liquid nitrogen, and then placing the frozen microspheres in a freeze dryer for freeze drying for 20-24 hours to obtain the hydrogel.
9. The method for preparing the hydrogel according to claim 7, wherein the air drying comprises the following specific steps: and (3) drying the microspheres in a blast drying oven at the temperature of 60-70 ℃ for 20-24 hours to obtain the microsphere.
10. The sodium alginate-based nano-red titanium manganese ore/lignite-based active coke hydrogel prepared by the preparation method of the hydrogel according to any one of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911354045.8A CN111001393B (en) | 2019-12-24 | 2019-12-24 | Sodium alginate-based nano-supported red titanium manganese ore/lignite-based active coke hydrogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911354045.8A CN111001393B (en) | 2019-12-24 | 2019-12-24 | Sodium alginate-based nano-supported red titanium manganese ore/lignite-based active coke hydrogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111001393A true CN111001393A (en) | 2020-04-14 |
| CN111001393B CN111001393B (en) | 2023-05-23 |
Family
ID=70117923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911354045.8A Active CN111001393B (en) | 2019-12-24 | 2019-12-24 | Sodium alginate-based nano-supported red titanium manganese ore/lignite-based active coke hydrogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111001393B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115518624A (en) * | 2022-10-14 | 2022-12-27 | 陕西科技大学 | Coal waste adsorption gel ball containing ZIF structure and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005218956A (en) * | 2004-02-05 | 2005-08-18 | Japan Organo Co Ltd | Photocatalyst-containing porous granular body and manufacturing method therefor |
| CN101579643A (en) * | 2009-06-11 | 2009-11-18 | 湖州师范学院 | Sol-gel in situ preparation method of titanium dioxide nano powder coated with alginate |
| CN101640262A (en) * | 2008-07-31 | 2010-02-03 | 深圳市比克电池有限公司 | Anode material of lithium ion battery |
| CN103464217A (en) * | 2013-09-13 | 2013-12-25 | 天津工业大学 | Alginate-based composite hydrogel catalytic membrane of renewable catalyst and preparation method thereof |
| CN105536726A (en) * | 2016-02-03 | 2016-05-04 | 上海应用技术学院 | Preparation method of oxidized graphene and sodium alginate composite absorbing material capable of removing ciprofloxacin in aqueous solution |
| US20180221543A1 (en) * | 2016-08-19 | 2018-08-09 | B.J. Zh. F. Panther Medical Equipment Co. Ltd. | Titanium nail capable of loading drug and drug-loaded titanium nail and preparing method of the same |
| CN109126647A (en) * | 2018-09-08 | 2019-01-04 | 佛山市森昂生物科技有限公司 | A kind of preparation method of graphene oxide-sodium alginate gel ball |
| CN109464989A (en) * | 2018-11-23 | 2019-03-15 | 上海海洋大学 | A kind of preparation method of sodium alginate gel ball |
| CN109529771A (en) * | 2019-01-11 | 2019-03-29 | 北方工业大学 | In-situ self-regeneration adsorbent and preparation method thereof |
| CN109759132A (en) * | 2019-02-20 | 2019-05-17 | 吉林建筑大学 | The preparation method and composite photocatalyst gel ball of composite photocatalyst gel ball |
-
2019
- 2019-12-24 CN CN201911354045.8A patent/CN111001393B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005218956A (en) * | 2004-02-05 | 2005-08-18 | Japan Organo Co Ltd | Photocatalyst-containing porous granular body and manufacturing method therefor |
| CN101640262A (en) * | 2008-07-31 | 2010-02-03 | 深圳市比克电池有限公司 | Anode material of lithium ion battery |
| CN101579643A (en) * | 2009-06-11 | 2009-11-18 | 湖州师范学院 | Sol-gel in situ preparation method of titanium dioxide nano powder coated with alginate |
| CN103464217A (en) * | 2013-09-13 | 2013-12-25 | 天津工业大学 | Alginate-based composite hydrogel catalytic membrane of renewable catalyst and preparation method thereof |
| CN105536726A (en) * | 2016-02-03 | 2016-05-04 | 上海应用技术学院 | Preparation method of oxidized graphene and sodium alginate composite absorbing material capable of removing ciprofloxacin in aqueous solution |
| US20180221543A1 (en) * | 2016-08-19 | 2018-08-09 | B.J. Zh. F. Panther Medical Equipment Co. Ltd. | Titanium nail capable of loading drug and drug-loaded titanium nail and preparing method of the same |
| CN109126647A (en) * | 2018-09-08 | 2019-01-04 | 佛山市森昂生物科技有限公司 | A kind of preparation method of graphene oxide-sodium alginate gel ball |
| CN109464989A (en) * | 2018-11-23 | 2019-03-15 | 上海海洋大学 | A kind of preparation method of sodium alginate gel ball |
| CN109529771A (en) * | 2019-01-11 | 2019-03-29 | 北方工业大学 | In-situ self-regeneration adsorbent and preparation method thereof |
| CN109759132A (en) * | 2019-02-20 | 2019-05-17 | 吉林建筑大学 | The preparation method and composite photocatalyst gel ball of composite photocatalyst gel ball |
Non-Patent Citations (4)
| Title |
|---|
| EL-FADL: "Synthesis of nanocomposite membranes and their application in photocatalytic process for organic pollutions removal from groundwater, East Nile Delta, Egypt", 《DESALINATION AND WATER TREATMENT》, vol. 55, 11 September 2015 (2015-09-11), pages 2951 - 2961 * |
| 李若征等: "活性焦吸附-曝气生物滤池处理煤气化废水生化出水", 《化工环保》 * |
| 李若征等: "活性焦吸附-曝气生物滤池处理煤气化废水生化出水", 《化工环保》, vol. 37, 15 October 2017 (2017-10-15), pages 514 - 518 * |
| 陈海峰: "海藻酸盐包覆二氧化钛微球的制备与其光催化性能", 《稀有金属材料与工程》, vol. 39, 15 August 2010 (2010-08-15), pages 306 - 309 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115518624A (en) * | 2022-10-14 | 2022-12-27 | 陕西科技大学 | Coal waste adsorption gel ball containing ZIF structure and preparation method and application thereof |
| CN115518624B (en) * | 2022-10-14 | 2023-11-17 | 陕西科技大学 | ZIF structure-containing coal waste adsorption gel ball and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111001393B (en) | 2023-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113559824B (en) | Nitrogen-doped porous carbon material adsorbent for treating dye wastewater and preparation method and application thereof | |
| CN107413295B (en) | Preparation method of porous active carbon nanofiber loaded hydroxyapatite defluorination material | |
| CN112156752A (en) | Modified activated carbon with reproducible adsorbability and application thereof in wastewater treatment | |
| CN112774646A (en) | Preparation method of activated carbon capable of regenerating and adsorbing methyl orange dye | |
| CN107573457B (en) | Porous interpenetrating network poly N-isopropylacrylamide/zirconium alginate gel ball and preparation method and application thereof | |
| CN114797781A (en) | Preparation method of lanthanum-loaded nitrogen-doped porous carbon-phosphorus adsorption material | |
| CN111001393A (en) | Sodium alginate-based loaded nano-red titanium manganese ore/brown coal-based active coke hydrogel and preparation method thereof | |
| CN110841595A (en) | Preparation method and application of nitrogen-doped graphitized carbon material | |
| CN111036176A (en) | Magnetic graphene oxide/sodium alginate/sodium carboxymethylcellulose composite material and preparation method thereof | |
| CN107442066B (en) | Microwave carbonized persimmon peel biological adsorbent and preparation method and application thereof | |
| CN113426385A (en) | Carbon aerogel pellet, preparation method thereof and application of carbon aerogel pellet as heavy metal adsorption material | |
| CN111036179B (en) | Composite hydrogel and preparation method thereof | |
| CN112755974A (en) | SCP @ PEI composite hydrogel ball and preparation method and application thereof | |
| CN116459795A (en) | Water treatment material for removing lead from wastewater and preparation method and application thereof | |
| CN116618028A (en) | Aerogel type MoS 2 Composite adsorbent, preparation method thereof and application thereof in wastewater treatment | |
| CN114558558B (en) | Double-crosslinked hydrogel doped with attapulgite as well as preparation method and application thereof | |
| CN116116388A (en) | Preparation method and application of biochar/magnesium aerogel bead dephosphorization adsorbent | |
| CN111848972B (en) | Preparation method and application of bimetallic MOF based on MOF-808 | |
| He et al. | Poly (ethyleneimine) functionalized organic-inorganic hybrid silica by hydrothermalassisted surface grafting method for removal of nickel (II) | |
| CN113171758B (en) | Carbon dioxide adsorbent and preparation method and application method thereof | |
| CN110975798B (en) | Preparation method, application and regeneration method of FeO (OH) -diatomite composite adsorbent | |
| CN115106065A (en) | Gel ball adsorption material and preparation method and application thereof | |
| KR101683834B1 (en) | Ni/ACTIVATED CARBON AEROGEL COMPOSITE FOR HYDROGEN STORAGE AND METHOD OF MANUFACTURING THEREOF | |
| CN108772050B (en) | Adsorbent, preparation method and application thereof | |
| TWI643815B (en) | Method for preparing high specific surface area sewage sludge carbon material, active carbon material and the use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |