CN106268618A - A kind of preparation method and applications of active adsorbing material - Google Patents
A kind of preparation method and applications of active adsorbing material Download PDFInfo
- Publication number
- CN106268618A CN106268618A CN201610797897.4A CN201610797897A CN106268618A CN 106268618 A CN106268618 A CN 106268618A CN 201610797897 A CN201610797897 A CN 201610797897A CN 106268618 A CN106268618 A CN 106268618A
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- preparation
- adsorbing material
- active adsorbing
- anaerobic
- water
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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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Abstract
The invention discloses the preparation method of a kind of active adsorbing material, comprise the following steps: 1) clean porous carrier materials；2) weigh iron chloride and ferrous sulfate is dissolved in anaerobic water, be configured to slaine mixed liquor；3) by cleaned carrier material, anaerobic deionized water and slaine mixed liquor mix and blend water bath with thermostatic control, drip ammonia spirit, after dripping ammonia spirit, continue stirring 20～30 minutes；4) after completion of the reaction, filter under oxygen free condition, clean with anaerobic deionized water, be dried.The preparation technology of the present invention is simple, and mild condition operates fast and convenient, low cost, it is easy to industrialized production.The adsorbing material prepared according to the method, by Adsorption of Organic to repair materials surface, and can add dual oxide solution and can realize the regeneration of adsorbing material.
Description
Technical field
The invention belongs to technical field of function materials, be specifically related to one and there is oxidability rain water pollutant adsorption material
The preparation method of material.
Background technology
The pollution problem that China's rainfall runoff causes is the most serious, and the important lake in Taihu Lake, Dian Chi etc., rainwater causes
Non-point pollution has become the one of the main reasons of water quality deterioration.Rainfall runoff carries a large amount of pollutant and enters urban water system and also make
Become severe contamination.Preliminary conservative estimation, city rainwater runoff pollution accounts for the ratio of water pollution load, at present Beijing and on
Sea accounts for about 10%.It is true that consider noncontinuity and burst, its pollutional load proportion of Runoff contaminants conveying
Can raise at double within the short time interval in rainy season, exceed point-source pollution, impacting property of urban water-body be affected, seriously restricts city
The thorough improvement of quality of water environment, the water contamination accident occurred after many urban storms is all good illustration.Nearly twenty or thirty year
Between, urban rainwater pollutes and receives significant attention in developed country.
Using adsorbing material that wherein pollutant carry out absorption after filtering rainfall is to remove organic contamination in rainwater
A kind of effective ways of thing purifying rainwater water quality.Currently used adsorbing material is of a great variety, active charcoal, activated alumina,
Silica gel, molecular sieve etc..But, just become after material absorption is saturated and lose absorbability and reformed into solid waste, even
Secondary pollution can be formed.Therefore, the adsorbing material of a kind of rain water pollutant with recycling ability is needed badly.
Summary of the invention
It is an object of the invention to overcome the shortcoming of prior art, it is provided that one has Regenerated energy
The preparation method of the adsorbing material of power.
The technical solution used in the present invention is: the preparation method of a kind of active adsorbing material, comprises the following steps:
1) porous carrier materials is cleaned；
2) weigh iron chloride and ferrous sulfate is dissolved in anaerobic water, be configured to slaine mixed liquor；
3) by cleaned carrier material, anaerobic deionized water and slaine mixed liquor mix and blend water bath with thermostatic control, dropping
Ammonia spirit, continues stirring 20～30 minutes after dripping ammonia spirit；
4) after completion of the reaction, filter under oxygen free condition, clean with anaerobic deionized water, be dried.
Preferably, the method cleaning porous carrier materials is: first with after soak with hydrochloric acid, be placed in anaerobic water by this material
Supersound process, is carried out.
It is further preferred that concentration of hydrochloric acid solution is 3%～5%.
Preferably, porous material is activated carbon, silica gel, any one in molecular sieve.
Preferably, n (Fe in slaine mixed liquor3+): n(Fe2+)=(2～3): 1.
Preferably, ammonia spirit rate of addition is 0.6mL/min～1mL/min, persistently drips 30 min.
It is further preferred that the concentration of ammonia spirit is 28%～30%.
Preferably, carrier material: ferrous sulfate: the mass ratio of iron chloride is 30:6:17.
A kind of adsorbing material prepared according to the preparation method of active adsorbing material, its absorbability reaches saturated rear addition
Hydrogen peroxide can recover absorbability.
The application in municipal sewage treatment of the preparation method of a kind of active adsorbing material.
The invention has the beneficial effects as follows:
(1) preparation technology of the present invention is simple, and mild condition operates fast and convenient, low cost, it is easy to industrialized production.
(2) use adsorbing material prepared by the present invention to have irregular loose structure so that it is with after contacting rain water wherein
Organic pollution can be adsorbed to repair materials surface, and add dual oxide solution and oxidation operation can be realized adsorption material
The regeneration of material.
Accompanying drawing explanation
Fig. 1 is infrared ray (FTIR) figure of the active carbon adsorption material prepared；
Fig. 2 is X-ray diffraction (XRD) figure of the active carbon adsorption material prepared；With oxidisability activated carbon XRD figure；
Fig. 3 is scanning electron microscope (SEM) figure of the active carbon adsorption material prepared；
Fig. 4 is the adsorption curve of the active carbon adsorption material prepared；
Fig. 5 is Langmuir and the Freundlich adsorption curve of the active carbon adsorption material prepared
Fig. 6 is the oxidation curve of the active carbon adsorption material prepared；
Fig. 7 is the recycling figure of the active carbon adsorption material prepared.
Detailed description of the invention
The preparation of embodiment 1 active carbon adsorption material
Take 300 mL deionized waters to be placed in the there-necked flask of 1000 mL, be positioned over the water bath with thermostatic control of 80 DEG C, use purity nitrogen to expose
Gas 30 min is to remove dissolved oxygen therein；Hydrochloric acid solution with 5% soaks 30g activated carbon, adsorbing material is placed on anaerobic and goes
Ionized water uses the ultrasound wave of frequency 50 Hz, cleans 10 min, then clean 3 times with anaerobic deionized water, make carrier；Weigh
6g ferrous sulfate and 17g iron chloride are dissolved in anaerobic deionized water, are sufficiently stirred for；Cleaned adsorbing material is joined three mouthfuls
In Ping, use automatic stirrer to be stirred continuously and maintain the water bath with thermostatic control of 80 DEG C with constant speed, use automatic liquid adding device with 0.6mL/
The nominal rated speed of min drips the ammonia spirit that concentration is 30% in there-necked flask, drips 30min, continues after dripping ammonia spirit
Stirring 30min；After completion of the reaction, there-necked flask is transferred in anaerobic case, uses glass fiber filter paper to be carried out by adsorbing material
Filter, then uses anaerobic deionized water to clean 3 times, is finally positioned over natural drying 24 hours in anaerobic case；Dried absorption
Material, uses brown port grinding bottle to preserve.
The preparation of embodiment 2 silica gel adsorptive material
Take 400 mL deionized waters to be placed in the there-necked flask of 1000 mL, be positioned over the water bath with thermostatic control of 70 DEG C, use purity nitrogen to expose
Gas 30 min is to remove dissolved oxygen therein；Hydrochloric acid solution with 5% soaks 30g silica gel, and silica gel is placed on anaerobic deionized water
The ultrasound wave of middle use frequency 60 Hz, cleans 20min, then cleans 3 times with anaerobic deionized water, make carrier；Weigh 6g sulphuric acid sub-
Ferrum and 17g iron chloride are dissolved in anaerobic deionized water, are sufficiently stirred for；Cleaned adsorbing material is joined in there-necked flask, adopts
It is stirred continuously and maintains the water bath with thermostatic control of 70 DEG C with automatic stirrer with constant speed, use specified with 1mL/min of automatic liquid adding device
Speed drips the ammonia spirit that concentration is 28% in there-necked flask, drips 30min, continues stirring after dripping ammonia spirit
30min；After completion of the reaction, there-necked flask is transferred in anaerobic case, uses glass fiber filter paper to be filtered by adsorbing material, so
Rear employing anaerobic deionized water cleans 4 times, is finally positioned over natural drying 20 hours in anaerobic case；Dried adsorbing material,
Employing brown port grinding bottle preserves.
Experimental example
1) infared spectrum with oxidability activated carbon prepared
Preparation in embodiment 1 is had oxidability activated carbon suction adsorbing material and carries out infared spectrum detection.As it is shown in figure 1,
At 3400 cm-1Place strong absworption peak be that O-H(includes water, carboxyl compound, phenols or the hydroxyl of alcohol apoplexy due to endogenous wind) stretching vibration
Causing, compared with activated carbon collection of illustrative plates, activated carbon/iron oxides is at 3400 cm-1The absorbance at peak, place strengthens, and this has been probably
The O-H stretching vibration of the iron oxides of load produces.At 567 cm-1There are strong absworption peak, 746 cm in place-1With 885 cm-1Place also goes out
Existing Fe-O peak, the existence of iron oxides in this illustrative material.From Fig. 2 XRD figure compose, the adsorbing material of preparation except
26.6 ° it can be seen that significantly outside activated carbon diffraction maximum, have obvious diffraction maximum at 35.5 °, 43.3 °, 57.6 ° and 62.9 °,
It is Fe3O4With γ-Fe2O3Characteristic diffraction peak, due to ferrous existence, under the existence condition having oxidant hydrogen peroxide just
The adsorbing material that can make preparation has oxidability；From figure 3, it can be seen that the glossiness of activated carbon is more consistent, surface does not connects
Be dispersed with the pore structure that plays a major role of absorption continuously, preparation there is oxidability activated carbon due to the existence of iron oxides
And the modal change of adsorbing material caused, tiny iron oxide nanoparticles is supported on activated carbon surface brokenly
On, cause surface texture to present rough shape, and between granule, there is a large amount of gap, and this must be conducive to pollutant
Absorption.
2) material is to organic absorbability
Preparation in embodiment 1 is had oxidability activated carbon suction adsorbing material and carries out absorbability detection.Can be seen by Fig. 4
Going out, the activated carbon with oxidability of preparation is through the 4-chlorophenol of the adsorption test adsorbable 32% of 6h.Its adsorption process can be divided
Being two stages, first stage is the quick adsorption stage, can realize the absorbability of adsorbing material 84% within the time of 4h,
Second stage is absorption phase at a slow speed, and through the adsorption reaction of 96h, adsorbing material progressivelyes reach adsorption equilibrium.Such as Fig. 5 institute
Showing, the adsorbing material of preparation meets Langmuir and Freundlich model to the adsorption process of 4-chlorophenol.
3) material is to organic oxidability
Preparation in embodiment 1 is had oxidability activated carbon and inhales the oxidability detection of adsorbing material.Activity by preparation
Charcoal joins in the 4-chlorophenol solution configured, and solution is adjusted to acid ph value, and < 5, addition hydrogen peroxide solution, course of reaction is such as
Shown in Fig. 6.Through the adsorption reaction of 4h, adsorbing material reaches balance to the absorption of 4-chlorophenol, adds after hydrogen peroxide solution 95%
4-chlorophenol is removed, and the 4-chlorophenol solution concentration adding unsupported iron oxides activated carbon contrasted with this is not sent out after 4h
Raw notable change, illustrates that the activated carbon of supported ferriferous oxide has notable oxidability, in an acidic solution, its carrier surface
Iron oxides and hydrogen peroxide are by the oxidation operation on its surface so that it is again have absorbability.As it is shown in fig. 7, the work of preparation
Property charcoal adsorbing material through 5 times recycle, remain to remove the 4-chlorophenol of 85%, illustrate prepare activated carbon have renewable heavy
The multiple ability utilized.
Claims (10)
1. a reproducible active adsorbing material preparation method, comprises the following steps:
1) porous carrier materials is cleaned；
2) weigh iron chloride and ferrous sulfate is dissolved in anaerobic water, be configured to slaine mixed liquor；
3) by cleaned carrier material, anaerobic deionized water and slaine mixed liquor mix and blend water bath with thermostatic control, dropping
Ammonia spirit, continues stirring 20～30 minutes after dripping ammonia spirit；
4) after completion of the reaction, filter under oxygen free condition, clean with anaerobic deionized water, be dried.
The preparation method of active adsorbing material the most according to claim 1, it is characterised in that described cleaning porous carrier material
The method of material is: first with after soak with hydrochloric acid, this material is placed on supersound process in anaerobic water, is carried out.
The preparation method of active adsorbing material the most according to claim 2, it is characterised in that described concentration of hydrochloric acid solution is
3%～5%.
The preparation method of active adsorbing material the most according to claim 1, it is characterised in that described porous material is activity
Charcoal, silica gel, any one in molecular sieve.
The preparation method of active adsorbing material the most according to claim 1, it is characterised in that in described slaine mixed liquor
n(Fe3+): n(Fe2+)=(2～3): 1.
The preparation method of active adsorbing material the most according to claim 1, it is characterised in that described ammonia spirit dropping speed
Degree is 0.6mL/min～1mL/min, persistently drips 30 min.
The preparation method of active adsorbing material the most according to claim 1, it is characterised in that the concentration of described ammonia spirit
It is 28%～30%.
The preparation method of active adsorbing material the most according to claim 1, it is characterised in that described carrier material: sulphuric acid
Ferrous: the mass ratio of iron chloride is 30:6:17.
9. the suction prepared according to the preparation method of the active adsorbing material described in any one claim in claim 1～8
Enclosure material, it is characterised in that the absorbability of adsorbing material reaches the saturated rear hydrogen peroxide that adds can recover absorbability.
10. the preparation method according to the active adsorbing material described in any one claim in claim 1～8 is dirty in city
Application in water process.
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| CN201610797897.4A CN106268618A (en) | 2016-08-31 | 2016-08-31 | A kind of preparation method and applications of active adsorbing material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320318A (en) * | 2020-03-19 | 2020-06-23 | 烟台金正环保科技有限公司 | Zero-emission advanced treatment process for RO (reverse osmosis) concentrated water |
| CN113694886A (en) * | 2021-07-28 | 2021-11-26 | 广东建科创新技术研究院有限公司 | Magnetic adsorption material with Fenton oxidation catalysis function and preparation method and application thereof |
| CN114436429A (en) * | 2021-12-17 | 2022-05-06 | 广东建科创新技术研究院有限公司 | Adsorption and catalytic oxidation process for organic pollutants in water body |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915849A (en) * | 2006-09-07 | 2007-02-21 | 上海交通大学 | Method for preparing composite assembled object of magnetic ferriferous oxide/ molecular sieve of Nano zeolite |
| CN102151543A (en) * | 2011-03-16 | 2011-08-17 | 浙江大学 | Preparation method, product and application of catalytic activity nano particle loaded absorbent |
| CN104438312A (en) * | 2014-11-14 | 2015-03-25 | 华中科技大学 | Restoration method of severely combined pollution site |
| CN105126755A (en) * | 2015-09-10 | 2015-12-09 | 哈尔滨工业大学宜兴环保研究院 | Novel magnetic active carbon and preparation method thereof |
| CN105439238A (en) * | 2015-12-11 | 2016-03-30 | 哈尔滨工业大学宜兴环保研究院 | Method for integrated treatment of dyeing wastewater by using magnetic activated carbon |
-
2016
- 2016-08-31 CN CN201610797897.4A patent/CN106268618A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915849A (en) * | 2006-09-07 | 2007-02-21 | 上海交通大学 | Method for preparing composite assembled object of magnetic ferriferous oxide/ molecular sieve of Nano zeolite |
| CN102151543A (en) * | 2011-03-16 | 2011-08-17 | 浙江大学 | Preparation method, product and application of catalytic activity nano particle loaded absorbent |
| CN104438312A (en) * | 2014-11-14 | 2015-03-25 | 华中科技大学 | Restoration method of severely combined pollution site |
| CN105126755A (en) * | 2015-09-10 | 2015-12-09 | 哈尔滨工业大学宜兴环保研究院 | Novel magnetic active carbon and preparation method thereof |
| CN105439238A (en) * | 2015-12-11 | 2016-03-30 | 哈尔滨工业大学宜兴环保研究院 | Method for integrated treatment of dyeing wastewater by using magnetic activated carbon |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320318A (en) * | 2020-03-19 | 2020-06-23 | 烟台金正环保科技有限公司 | Zero-emission advanced treatment process for RO (reverse osmosis) concentrated water |
| CN113694886A (en) * | 2021-07-28 | 2021-11-26 | 广东建科创新技术研究院有限公司 | Magnetic adsorption material with Fenton oxidation catalysis function and preparation method and application thereof |
| CN114436429A (en) * | 2021-12-17 | 2022-05-06 | 广东建科创新技术研究院有限公司 | Adsorption and catalytic oxidation process for organic pollutants in water body |
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Application publication date: 20170104 |