CN108404857A - A kind of the porous ceramic grain sorbing material and preparation method of load hydrated metal oxide - Google Patents
A kind of the porous ceramic grain sorbing material and preparation method of load hydrated metal oxide Download PDFInfo
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- CN108404857A CN108404857A CN201810258831.7A CN201810258831A CN108404857A CN 108404857 A CN108404857 A CN 108404857A CN 201810258831 A CN201810258831 A CN 201810258831A CN 108404857 A CN108404857 A CN 108404857A
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- porous ceramic
- ceramic grain
- metal oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- Life Sciences & Earth Sciences (AREA)
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of porous ceramic grains and preparation method thereof of load hydrated metal oxide, belong to engineering of water treatment Material Field.The material is using porous ceramic grain as skeleton, and using hydrated metal oxide as active adsorbing material, grain size is 0.1mm~1cm, and specific surface area is 10~1000m2/g, and the load capacity of average pore size 5nm~500nm, hydrated metal oxide are calculated as 2mg/g~200mg/g with metal.The Core Production Technology flow of the material includes：Porous ceramic grain is put into lye and is activated；The porous ceramic grain of activation is put into dipping in the solution of metal salt and absorbs metal ion；The porous ceramic grain of gained absorption metal ion is put into lye and is reacted, is rinsed, you can obtain the porous ceramic grain of load hydrated metal oxide.The porous ceramic grain of load hydrated metal oxide provided by the invention can be used as high-performance sorbing material to be applied to field of environment engineering, the pollutant in Adsorption water.
Description
Technical field
The invention belongs to water-treatment technology fields, and in particular to a kind of to be answered by what hydrated metal oxide and porous ceramic grain were constituted
Close nano-porous materials and preparation method.
Background technology
Hydrated metal oxide material one side surface band can adsorb band xenogenesis charge compared with multi-charge by electrostatic attraction
Pollutant on the other hand the multiple pollutant in coordination atom and water body can be provided and form the pollution of coordinate bond Adsorption
Object, such as phosphate anion, arsenic acid radical ion, the anionic pollutants such as fluorine ion, Pb, Cd, the heavy metal contaminants such as Hg, Cu.Water
Metal oxide nano-material is closed because grain size is in nanometer scale, large specific surface area, activity is strong, has more excellent adsorptivity
Energy.For example, paper (Chen Hui waits organic polymers load hydrated ferric oxide to remove micro-antimony in water removal, Chinese water supply and drainage,
2017,13 (33)：It 68-72) has studied the load of chitosan/acetic acid cellulose and is hydrated ferric oxide multi-porous compound adsorbent to micro- in water
Measure the absorption property of antimony.In addition, hydrated metal oxide material can be used as class Fenton catalysis of solid catalyst hydrogen peroxide, over cure
The decomposition such as hydrochlorate, ozone generate strong oxidizing property free radical, oxidative degradation organic pollution.For example, (hydrated ferric oxide is catalyzed paper
Ozone oxidation removes underwater trace nitrobenzene, environmental science, 2004,25 (4)：43-47) report hydrated ferric oxide catalysis ozone
The performance of oxidative degradation underwater trace nitrobenzene.Although hydrated metal oxide material has excellent absorption, catalytic performance,
It is that hydrated metal oxide material particle size is small, in the case of large-scale use, is easy to run off, effluent color dilution is made to increase.In addition hydration gold
Belong to oxide and be easy when being used in wastewater media hardened, so that head loss is increased, filterability decline.Pass through carrier loaded water
Conjunction metal oxide, which prepares bulky grain absorption or catalysis material, can reduce loss of the hydrated metal oxide in water purification process
And filtration resistance.For example, patent (Pan Bingcai waits a kind of environmental functional composite materials based on nano granule inorganic functional agent of,
CN101143311 a kind of environmental functional composite material based on organic macroreticular resin and nano inorganic functional agent) is disclosed.Patent
(Pan Bingcai waits environment functional materials and preparation method thereof of the based on nanoparticles hydrated manganese oxide, CN101224408A) is open
A kind of ion exchange organic resin loads the synthetic method of nano hydrated manganese oxide composite material.
Porous ceramic grain is that it is de- to add a small amount of bentonite, illiteracy based on the natural porous materials such as diatomite, volcanic rock, zeolite
The clay materials such as stone, convex-concave stick stone are auxiliary bonding agent, the grade inorganic non-metallic porous material obtained through high-temperature calcination.It is more
Hole haydite itself can be used as sorbing material, the cationics such as Adsorption ammonia nitrogen, heavy metal pollutant and part organic contamination
Object has been applied to waste water control, the field of environment engineering such as air purification.For example, (salinity is to coal in artificial filtration system for paper
The influence of slag and haydite dephosphorization process, environmental project journal, 2015,9 (10)：Haydite 4705-4710) is reported manually to be percolated
Phosphorus removal property in system.But porous ceramic grain activity itself ingredient is few, activity is low, especially to anionic property pollutant removal
Performance is bad.Load nano active ingredient be improve haydite absorption, catalytic performance effective ways.For example, patent (thank to hair,
A kind of porous phosphorus removing haydites of equal and preparation method thereof, CN104876639A) using concavo-convex rod soil as haydite aggregate, lanthanum carbonate is to inhale
Attached phosphorus active constituent, agricultural crop straw are pore creating material, and porous phosphorus removing haydite is prepared for by high-temperature burning process.Paper (oxidation
The preparation of magnesium/subway dregs composite haydite and phosphorus removal property research, using chemical industry, 2015,44 (9):1581-1585) with discarded
Subway dregs is primary raw material, and dephosphorization haydite is prepared for by auxiliary material of magnesia.
Although in short, currently, existing exclusive use hydrated metal oxide or porous ceramic grain for sewage Adsorption or
The relevant report of catalyzing oxidizing degrading pollutant, but the product of the porous ceramic grain using load hydrated metal oxide is not found
And synthetic method.In order to overcome the shortcomings of hydrated metal oxide material and porous ceramic grain, hydrated metal oxide is organically combined
The high activity of material and the large scale of porous ceramic grain, how mesoporous advantage, the present invention are skeleton with porous ceramic grain, absorb metal ion
After solution, through in-situ precipitate technique under alkaline environment, the porous ceramic grain product of load hydrated metal oxide is prepared.
Invention content
The object of the present invention is to provide the porous ceramic grain composite materials and its system of load hydrated metal oxide-based nanomaterial
Preparation Method comprehensively utilizes large scale, the how mesoporous advantage of the high activity and porous ceramic grain of hydrated metal oxide nano material, is
The sorbing material that the removal of environmental contaminants is had excellent performance using offer.The product of the present invention is a kind of load hydrated ferric oxide,
Hydrated alumina, hydrated manganese oxide, the porous ceramic grain of the hydrated metal oxides nano-particle such as hydrous zirconium oxide(HZO).The present invention also relates to
And the production method of the porous ceramic grain of load hydrated metal oxide-based nanomaterial.This method is to impregnate, be precipitated as main technique
Feature.
The preparation method of the porous ceramic grain of the load hydrated metal oxide of the present invention, includes the following steps：
(a) it will make by oneself or commercially available porous ceramic grain is impregnated in lye, activated；
(b) dissolution of raw material based on water-soluble metal salt salt is prepared into hydrated metal oxide precursor solution；
(c) certain time will be impregnated in hydrated metal oxide precursor solution that porous ceramic grain is put into step (b)；
(d) by the porous ceramic grain in step (c), filtering is dried to obtain the porous ceramic grain of impregnating metal ion；
(e) porous ceramic grain of the impregnating metal ion of gained in step (d) is put into lye and is reacted, through washing, obtained
Load the porous ceramic grain of hydrated metal oxide.
(f) step (a) is optional step, and the porous ceramic grain surface by step (a) activation has more active hydroxyls
Base can improve the load capacity of hydrated metal oxide nano material.But not activated porous ceramic grain is used, it can also be suitable
Profit obtains the load hydrated metal oxide porous ceramic grain of relatively low load capacity.
Advantageous effect
The oxide porous haydite nanocomposite of load hydrated metal prepared using the present invention is existed as sorbing material
It is mainly had the following advantages that in environmental project application：(1) porous ceramic grain raw material sources are wide, at low cost；(2) hydrated metal oxide
It is protected by haydite, product is not hardened, and head loss is small；(3) porous ceramic grain of load hydrated metal oxide is grade, is not easy
It is lost in；(4) porous ceramic grain of load hydrated metal oxide is free of organic principle, anti-oxidant, long lifespan；(5) water load alloy
The porous ceramic grain for belonging to oxide is free of harmful element, and material itself does not pollute the environment in use.
Specific implementation mode
It further illustrates the present invention by the following examples.
Embodiment 1：The porous Diatomite Ceramsite of load hydration iron oxide nano material
(1) iron chloride is prepared into hydrated ferric oxide precursor solution, holding a concentration of 1 mol/Ls of Fe with water dissolution, volume is
100 milliliters；
(2) commercially available, 1-2 millimeters of grain size 100 grams of mesoporous Diatomite Ceramsite, the hydrated ferric oxide being added in step 1 are taken
In precursor solution, oscillation is impregnated 10 minutes, is ultrasonically treated 10 minutes removal haydite bubbles；
(3) it is removed by filtration extra solution, is dried 1 hour through 105oC, drying is obtained, absorbs hydrated ferric oxide
The Diatomite Ceramsite of precursor；
(4) by the Diatomite Ceramsite for the absorption hydrated ferric oxide precursor that step (3) obtains be put into volume be 1 liter NaOH it is molten
It is impregnated 1 hour in liquid (0.1 mole/L).
(5) filtering removes extra NaOH solution, is washed to neutrality, obtains the porous silicon of load hydration iron oxide nano material
Diatomaceous earth haydite.
Embodiment 2：Load the porous Diatomite Ceramsite of hydrous zirconium oxide(HZO)
Iron chloride in 1 step 1 of embodiment is replaced with into zirconium acetate, concentration is adjusted to 0.2 mol/L, other steps are not
Become, you can obtain the porous Diatomite Ceramsite of load hydration nanometer zirconium oxide.
Embodiment 3：Load the porous Diatomite Ceramsite of hydrated manganese oxide
Iron chloride in 1 step of embodiment (1) is replaced with into manganese sulfate, other steps are constant, you can obtain load hydration
The porous Diatomite Ceramsite of nanometer zirconium oxide.
Claims (4)
1. it is main constitution element that the main component of the porous ceramic grain described in this patent, which is with Al, Si, O etc., tied containing duct
Structure, the clay that grain size is 0.1 millimeter to 1 centimetre is sintered inorganic non-metallic material, and such as using diatomite as primary raw material, addition is few
Measure bentonite, montmorillonite, the mesoporous Diatomite Ceramsite of the clay materials such as kaolin.
2. the hydrated metal oxide described in this patent refers to Fe, Mn, the water soluble salt of the metallic elements such as Zr is in alkaline environment water
The hydrated metal oxide that solution obtains, such as hydrated ferric oxide, hydrated alumina, hydrated manganese oxide, hydrous zirconium oxide(HZO) etc., addition are few
Other elements are measured, such as La, Ti, Ca, Si, P, F etc. can improve absorption property, also in the scope of this patent.
3. the porous ceramic grain of the load hydrated metal oxide described in this patent refers to by the haydite and right described in claim 1
It is required that the composite material that 2 hydrated metal oxides organically combine.
4. the preparation of the porous ceramic grain of hydrated metal oxide is loaded in the present invention characterized by impregnating, precipitate, under including mainly
Row specific steps：
(a) it will make by oneself or commercially available porous ceramic grain is impregnated in lye, activated；
(b) dissolution of raw material based on water-soluble metal salt salt is prepared into hydrated metal oxide precursor solution；
(c) certain time will be impregnated in hydrated metal oxide precursor solution that porous ceramic grain is put into step (b)；
(d) by the porous ceramic grain in step (c), filtering is dried to obtain the porous ceramic grain of impregnating metal ion；
(e) porous ceramic grain of the impregnating metal ion of gained in step (d) is put into lye and is reacted, through washing, loaded
The porous ceramic grain of hydrated metal oxide.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109107524A (en) * | 2018-09-28 | 2019-01-01 | 同济大学 | A kind of mud adsorbent and its preparation method and application |
| CN109675560A (en) * | 2018-12-29 | 2019-04-26 | 广州市金龙峰环保设备工程股份有限公司 | A kind of ceramsite catalyst and its preparation method and application that low-temperature plasma is modified |
| CN110575812A (en) * | 2019-09-25 | 2019-12-17 | 西南石油大学 | environment-friendly adsorbing material for efficient phosphorus removal of argil/pyrolusite and preparation method thereof |
| CN110713216A (en) * | 2019-10-24 | 2020-01-21 | 北京石油化工学院 | A multi-stage filtration system for high concentration oily sewage treatment |
| CN111054300A (en) * | 2019-12-19 | 2020-04-24 | 北京矿冶科技集团有限公司 | Magnetic adsorbent for treating heavy metal wastewater and preparation method thereof |
| CN111054301A (en) * | 2019-12-19 | 2020-04-24 | 北京矿冶科技集团有限公司 | Remediation method of heavy metal polluted surface water |
| CN111250033A (en) * | 2020-03-11 | 2020-06-09 | 安徽建筑大学 | Metal oxide porous micro-nano hierarchical structure modified honeycomb stone and preparation method and application thereof |
| CN111871359A (en) * | 2020-06-22 | 2020-11-03 | 浙江大学 | Zinc/iron layered double-metal hydroxide modified ceramsite and preparation and application methods thereof |
| CN113697945A (en) * | 2020-08-12 | 2021-11-26 | 南京大学 | Biomembrane reactor for deep purification of sewage and operation method thereof |
| CN113860907A (en) * | 2021-11-23 | 2021-12-31 | 华北电力大学 | Preparation method of lanthanum-aluminum bimetal modified bentonite ceramsite for water dephosphorization |
| CN114477554A (en) * | 2022-03-01 | 2022-05-13 | 合肥九号线传媒科技有限公司 | Wastewater treatment method based on iron-titanium composite oxide |
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Cited By (15)
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| CN109107524B (en) * | 2018-09-28 | 2020-05-08 | 同济大学 | Red mud adsorbent and preparation method and application thereof |
| CN109107524A (en) * | 2018-09-28 | 2019-01-01 | 同济大学 | A kind of mud adsorbent and its preparation method and application |
| CN109675560A (en) * | 2018-12-29 | 2019-04-26 | 广州市金龙峰环保设备工程股份有限公司 | A kind of ceramsite catalyst and its preparation method and application that low-temperature plasma is modified |
| CN110575812A (en) * | 2019-09-25 | 2019-12-17 | 西南石油大学 | environment-friendly adsorbing material for efficient phosphorus removal of argil/pyrolusite and preparation method thereof |
| CN110575812B (en) * | 2019-09-25 | 2022-03-22 | 西南石油大学 | Environment-friendly adsorbing material for efficient phosphorus removal of argil/pyrolusite and preparation method thereof |
| CN110713216A (en) * | 2019-10-24 | 2020-01-21 | 北京石油化工学院 | A multi-stage filtration system for high concentration oily sewage treatment |
| CN111054301A (en) * | 2019-12-19 | 2020-04-24 | 北京矿冶科技集团有限公司 | Remediation method of heavy metal polluted surface water |
| CN111054300A (en) * | 2019-12-19 | 2020-04-24 | 北京矿冶科技集团有限公司 | Magnetic adsorbent for treating heavy metal wastewater and preparation method thereof |
| CN111054301B (en) * | 2019-12-19 | 2023-04-18 | 北京矿冶科技集团有限公司 | Remediation method of heavy metal polluted surface water |
| CN111054300B (en) * | 2019-12-19 | 2023-04-18 | 北京矿冶科技集团有限公司 | Magnetic adsorbent for treating heavy metal wastewater and preparation method thereof |
| CN111250033A (en) * | 2020-03-11 | 2020-06-09 | 安徽建筑大学 | Metal oxide porous micro-nano hierarchical structure modified honeycomb stone and preparation method and application thereof |
| CN111871359A (en) * | 2020-06-22 | 2020-11-03 | 浙江大学 | Zinc/iron layered double-metal hydroxide modified ceramsite and preparation and application methods thereof |
| CN113697945A (en) * | 2020-08-12 | 2021-11-26 | 南京大学 | Biomembrane reactor for deep purification of sewage and operation method thereof |
| CN113860907A (en) * | 2021-11-23 | 2021-12-31 | 华北电力大学 | Preparation method of lanthanum-aluminum bimetal modified bentonite ceramsite for water dephosphorization |
| CN114477554A (en) * | 2022-03-01 | 2022-05-13 | 合肥九号线传媒科技有限公司 | Wastewater treatment method based on iron-titanium composite oxide |
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