CN106064044A - A kind of high osmosis demanganization filtrate and preparation method thereof and using method - Google Patents
A kind of high osmosis demanganization filtrate and preparation method thereof and using method Download PDFInfo
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- CN106064044A CN106064044A CN201610388822.0A CN201610388822A CN106064044A CN 106064044 A CN106064044 A CN 106064044A CN 201610388822 A CN201610388822 A CN 201610388822A CN 106064044 A CN106064044 A CN 106064044A
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- Prior art keywords
- demanganization
- filtrate
- scoria
- water
- manganese
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/06—Inorganic material, e.g. asbestos fibres, glass beads or fibres
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
-
- 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
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
Abstract
The invention discloses a kind of high osmosis demanganization filtrate preparation method, with scoria as raw material, with clean water scoria, remove its surface impurity, dry, cooling；Impregnating 1～48h with the HCl solution of 1～15% again, clear water is cleaned to neutrality, dries, cooling；After etching processing, scoria carries out the modification of KMnO4 solution surface, then dries, 240～350 DEG C of calcinations 1～5h in Muffle furnace, cooling；Finally rinse to going out clarification of water with clear water, dry, cooling, prepare novel demanganization filtrate and be applied to water body demanganization, it is achieved that the target of cost effective environmental protection demanganization.
Description
Technical field
The present invention relates to water body demanganization field, be specifically related to a kind of high osmosis demanganization filtrate and preparation method thereof and use
Method.
Background technology
The common quantivalence of manganese has+2 ,+4 ,+6 ,+7 four kinds of prices, wherein+6 valencys and+7 valency manganese in natural water general the most not
Stable, it is believed that do not exist in reality.+ 4 valency manganese are then often with solid matter (MnO2) and hydrate presented in water,
Its dissolubility is the lowest, and therefore+divalent manganese is dissolved in the main study subject that water is intended to remove.It is generally believed that the removal of manganese is wanted
More difficult than the removal of ferrum is many, because Fe2+At pH > can rapid oxidation be just Fe in the case of 7.03+, and Mn in water2+Then need to be
MnO could be oxidized to than relatively rapid during pH > 9.52Separate out.The pH value of subsoil water is typically below 7.5, as using autoxidation
Method is difficulty with except the such demanganization of ferrum.Therefore, the method for manganese in water body of removing at present is mainly physicochemical processing, example
Such as oxychloride and contact oxidation filtration etc..Although the efficiency of oxychloride is higher, but chlorine is easier to occur with the Organic substance in water
Reaction, thus produce secondary pollution.Therefore remove at the manganese that there is organic polluted underground water, be not suitable for using the method；And
Water adds the alkalization-Filtration of alkali, although it can reach the purpose of demanganization, but water outlet pH value to be improved, needs after acidifying
Can use；Membrane separation process and the physical method of ion exchange, show the fastest during the manganese in removing water body
Prompt, rapidly, but big by its early stage construction investment amount, the restriction of the shortcomings such as in running maintenance cost is high, also cannot be in economy
Low developed area is promoted；In contact oxidation filtration method, filled media generally utilizes the catalyst coating on its surface and water body
In manganese carry out chemical oxidation, and the oxide of manganese can be filtered.Wherein manganese ore is most widely used catalysis
Filter medium, the pH scope of application quick, economic and the broadest due to it and paid attention to by people.
2Fe (OH) is successfully being illustrated from the white academician of Lee's Gui from China3·2H2After O irony active filter film is except the mechanism of ferrum,
Illustrate filter for manganese removal too under the effect of " the manganese matter active filter film " of filter material surface, Mn2+Aoxidized by the dissolved oxygen in water
For MnO2, and adsorb at filter material surface, and make filter membrane be updated, this process is also self-catalyzed reaction, and its reaction equation is (4), (5)
Shown in:
Adsorption process:
Mn2++MnO2·xH2O→MnO2·MnO·(x-1)H2O+2H+ (4)
Oxidizing process:
2Mn2++(x-1)O2+4OH-→2MnOx·zH2O+2(1-z)H2O (5)
From the foregoing, it will be observed that the oxide (MnO of manganese2) Mn in removing water body2+During play adsorbing-oxidising effect.
But, manganese oxide typically occurs with weak crystalline mineral in nature, and it is mainly birnessite and vernadite (γ MnO2)。
Under normal circumstances, manganese oxide should be applied to Mn in water body with attritive powder or with the flocculate of hydroxide or the form of colloid2+
Removal.But due to individually using manganese oxide powder as demanganization filtrate, can be stranded by such as solid/liquid separation in demanganization processing procedure
Difficult, mass loss big and due to the impact of powder own characteristic (such as factors such as undefined structure, hyposmosis coefficients), seriously hinders
Hinder its application in terms of demanganization.
Manganese sand filtering material is to use high-quality natural manganese ores to process, and outward appearance is brown, it is possible to remove the ferrum in subsoil water
And manganese.But manganese sand price is higher, and it is generally required to just can possess satisfactory after the longer period of maturation (at least some months)
Demanganization effect, cause more filtrate to update and maintenance management expense, presenting so that the making of manganese sand in market of these problems
Consumption is greatly lowered year by year.
In order to solve this problem, preparing Coated With Manganese Oxide material on solid particulate matter can become a kind of efficient water
The method of demanganization in body.The solid particulate materials of report is mainly zeolite, quartz sand etc. at present.But, although zeolite surface is empty
Gap is many, specific surface area is big, can load more manganese by modified, but its mechanical strength is low, be not suitable for using for a long time.And
Although quartz sand disclosure satisfy that higher mechanical strength, but its surface is relatively smooth, specific surface area is little, and manganese load capacity relatively and is permeated
Coefficient is relatively low, there is also certain deficiency, reduces its application effect that manganese ion is removed in subsoil water.
This research is cheap and easy to get in view of scoria has, mechanical strength is high, surface pore (hole) big, infiltration coefficient is high
Advantage, by a series of modifying process, is carried on scoria surface by manganese matter active filter film, utilizes it to Mn in water2+Certainly urge
Oxidation, it is achieved to Mn in its subsoil water2+The purpose efficiently removed.
Contact oxidation method filter for manganese removal is used also to be respectively arranged with difference according to its processing maturation period of difference of filtrate at present, domestic external
Touch the startup of oxidation filter tank and the most all use nature immobilization, i.e. by the filtration self-assembling formation active filter film of manganese containing water, but this
Kind of method is very slow for the period of maturation of manganese matter active filter film, and relatively short also takes four or five months, the most then 1 year the most longer time
Between.Therefore the quick start method of contact oxidation method filter for manganese removal is used then to be particularly important.
Existing " quick start method of contact oxidation filter for manganese removal " patent, is with cheap fluvial sand as filler, to demanganization
Filter tank is injected the former water in manganese, uses the mode that interval is ozonation aerated, make divalent manganesetion in former water be oxidized to rapidly tetravalence
Water-fast compound is attached to grains of sand surface and forms manganese matter active filter film, and then forms manganese sand, has demanganization ability.But
The formation of this filtrate needs ozonation aerated, and this improves cost prepared by filtrate, and in Economic contrast backward areas, application is subject to
Limit, and the manganese matter active filter film adhesive force that surface is formed is spent little, it is impossible to bear excessive water velocity and backwash is strong
Degree.
In recent years, people begin one's study and replace manganese sand, such as fluvial sand with other filtrates.Permissible for filtrate with modified fluvial sand
Reduce cost, solve the problem that manganese sand mechanical strength is low.But, the removal of the bivalent manganese in subsoil water is imitated with fluvial sand for filtrate
Fruit is good not as manganese sand, and for the higher technique of some water yield demands, modified fluvial sand permeance property is relatively low.Therefore the present invention is at this
On the basis of improve, to preparing a kind of high osmosis demanganization filtering material safe, economic, efficient.
Summary of the invention
The purpose of the present invention is that provides a kind of high osmosis demanganization filtrate and preparation thereof to solve the problems referred to above
Method and using method, solution manganese sand cost is high, mechanical strength is low, the problem that fluvial sand removal efficiency is low, and it is big to have load capacity
The feature that infiltration coefficient is high.
For solving above-mentioned technical problem, a kind of high osmosis demanganization filtrate preparation method that the present invention proposes, including following
Preparation process:
(1) filtrate pretreatment: Fructus Crataegi clean water of getting fire, removes its surface impurity post-drying, cooling；
(2) filtrate etching processing: with 1～15% HCl solution pretreatment after scoria 1～48h, wash with clear water
Clean to neutrality, dry, cool down；
(3) filter material surface is granule modified；With 1～15%KMnO4 solution soaking 6～48h, after drying, in Muffle furnace
240～350 DEG C of calcinations 1～5h, finally cool down；
(4) filtrate cleans: rinses described modified scoria to after going out clarification of water with clear water, dries, cools down.
Preferably, the scoria particle diameter in described step (1) is 1-2mm.
Accordingly, the present invention also proposes a kind of high osmosis demanganization filtrate, with scoria as raw material, uses said method system
For forming.
Accordingly, also disclose a kind of method utilizing this filtrate to carry out water body demanganization, use said method to be prepared from
High osmosis demanganization filtrate carry out water body demanganization, it specifically includes following steps:
(1) in demanganization container, described demanganization filtrate is added；
(2) manganese containing water body is injected in described demanganization container；
(3) the regulation water body time of staying；
(4) measure the concentration of manganese in described manganese containing water body, after meeting concentration standard, terminate demanganization.
Having the beneficial effects that of the technique scheme of the present invention:
In such scheme, utilizing scoria as demanganization raw material, not only economy, raw material easily obtain, and meet
Certain mechanical strength, is greatly enhanced demanganization stability and accommodative ability of environment.
Accompanying drawing explanation
Scoria SEM figure before Fig. 1 is modification of filtration medium of the present invention, after modified and demanganization；
Fig. 2 be the present invention modified with demanganization after the Mapping figure of scoria surface Mn；
Fig. 3 be the present invention before modified, the EDS figure of scoria material surface after modified and demanganization；
Fig. 4 is the XRD figure of present invention filtrate before modified, after modified and demanganization；
Fig. 5 is the design sketch of modified filter material demanganization of the present invention.
Detailed description of the invention
For making the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and tool
Body embodiment is described in detail.
In order to reduce cost, improve water body demanganization efficiency and stability, propose a kind of high osmosis demanganization filtrate preparation side
Method, including following preparation process:
(1) filtrate pretreatment: Fructus Crataegi clean water of getting fire, removes its surface impurity post-drying, cooling；This step is main
It is to ensure that scoria surface cleaning, does not affect successive modified；
(2) filtrate etching processing: with 1～15% HCl solution pretreatment after scoria 1～48h, wash with clear water
Clean to neutrality, dry, cool down；This step make scoria surface area increase by HCl solution dipping such that it is able to bigger
The absorption demanganization filtering layer of degree, improves scoria service efficiency；
Wherein, HCl solution concentration can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%,
12%, 13%, 14% or 15%；
Wherein, the HCl solution pretreatment scoriaceous time can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h,
10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h、21h、22h、23h、24h、25h、26h、27h、28h、
29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h or
48h；
(3) filter material surface is granule modified；With 1～15%KMnO4Solution soaking 6～48h, after drying, in Muffle furnace
240～350 DEG C of calcinations 1～5h, finally cool down；This step utilizes KMnO4Decompose and be attached to scoria surface, thus carry out
Grain is modified；
Wherein, KMnO4The concentration of solution can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%,
11%, 12%, 13%, 14% or 15%；
Wherein, filtrate is with 1～15%KMnO4The time of solution soaking can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h,
9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h、21h、22h、23h、24h、25h、26h、27h、
28h、29h、30h、31h、32h、33h、34h、35h、36h、37h、38h、39h、40h、41h、42h、43h、44h、45h、46h、
47h or 48h；
Wherein, in Muffle furnace the temperature of calcination can be 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C,
300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C or 350 DEG C；
Wherein, in Muffle furnace, the time of calcination can be 1h, 2h, 3h, 4h or 5h；
(4) filtrate cleans: rinses described modified scoria to after going out clarification of water with clear water, dries, cools down.This step
Go out useless magazine, ultimately form demanganization filtrate.
Concrete, it is contemplated that improve filtrate permeability, improve filtrate and water body contact area, improve modified effect, choose
Scoriaceous particle diameter is 1-2mm.
Accordingly, utilize the high osmosis demanganization filtrate that said method prepares, there is permeability high, demanganization efficiency
Height, with low cost, the technical advantage such as easy acquisition.
As it is shown in figure 1, observe the surface before modified, after modified and demanganization under an electron microscope, it is possible to clearly
Finding, modified scoria surface roughness increases, and this causes due to organically-modified and granule modified, and at demanganization
After, its surface is the most roughening, and this adsorbs in a large number due to manganese ion and causes with manganese ion generation oxidation reaction with surface,
Also this change can be found clearly in conjunction with Fig. 2.
The present invention, for clear and definite demanganization method, it is further proposed that a kind of side utilizing this filtrate to carry out water body demanganization
Method, uses the high osmosis demanganization filtrate that is prepared from of said method to carry out water body demanganization, and it specifically includes following steps:
(1) in demanganization container, described demanganization filtrate is added；
(2) manganese containing water body is injected in described demanganization container；
(3) the regulation water body time of staying；
(4) measure the concentration of manganese in described manganese containing water body, after meeting concentration standard, terminate demanganization.
The method utilizes filtrate to carry out demanganization, and filtrate is high with the contact probability of water body, improve species activity accelerates reaction, carries
High demanganization ability, improves filtrate utilization rate.
The effect using said method to carry out demanganization may refer to accompanying drawing 3-5, and wherein accompanying drawing 3-4 shows, filter material surface manganese
Ion occurs in that after demanganization and significantly rises, and has adsorbed a large amount of manganese ion at filter material surface, and accompanying drawing 5 indicates more intuitively
The effect of this filtrate demanganization.
Such scheme medium to high permeable demanganization filtrate and preparation method thereof and using method so that water body demanganization technology obtains
Increase substantially, it is achieved that more environmentally friendly, more efficient.More stable demanganization effect, and raw material easily obtain, with low cost.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, on the premise of without departing from principle of the present invention, it is also possible to make some improvements and modifications, these improvements and modifications are also
Should be regarded as protection scope of the present invention.
Claims (4)
1. a high osmosis demanganization filtrate preparation method, including following preparation process:
(1) filtrate pretreatment: Fructus Crataegi clean water of getting fire, removes its surface impurity post-drying, cooling；
(2) filtrate etching processing: with 1～15% HCl solution pretreatment after scoria 1～48h, with clear water clean to
After neutrality, dry, cool down；
(3) filter material surface is granule modified；With 1～15%KMnO4 solution soaking 6～48h, after drying, in Muffle furnace 240～
350 DEG C of calcinations 1～5h, finally cool down；
(4) filtrate cleans: rinses described modified scoria to after going out clarification of water with clear water, dries, cools down.
High osmosis demanganization filtrate preparation method the most as claimed in claim, the scoria particle diameter in described step (1) is 1-
2mm。
3. a high osmosis demanganization filtrate, with scoria as raw material, uses method as claimed in claim 1 to be prepared from.
4. a water body demanganization method, uses high osmosis demanganization filtrate as claimed in claim 3, specifically includes following step
Rapid:
(1) in demanganization container, described demanganization filtrate is added；
(2) manganese containing water body is injected in described demanganization container；
(3) the regulation water body time of staying；
(4) measure the concentration of manganese in described manganese containing water body, after meeting concentration standard, terminate demanganization.
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| CN201610388822.0A CN106064044A (en) | 2016-06-03 | 2016-06-03 | A kind of high osmosis demanganization filtrate and preparation method thereof and using method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107285451A (en) * | 2017-03-24 | 2017-10-24 | 合肥供水集团有限公司 | It is a kind of for active filter of water treatment plant's catalysis oxidation demanganization and preparation method thereof |
| CN110548476A (en) * | 2019-09-30 | 2019-12-10 | 长春工业大学 | Preparation method and application of modified volcanic cinders filter material |
-
2016
- 2016-06-03 CN CN201610388822.0A patent/CN106064044A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 曲玉超: "改性火山渣陶粒去除废水中Cu(2+)/Ni(2+）离子的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 朱树阳: "改性河砂处理高锰地下水试验研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107285451A (en) * | 2017-03-24 | 2017-10-24 | 合肥供水集团有限公司 | It is a kind of for active filter of water treatment plant's catalysis oxidation demanganization and preparation method thereof |
| CN110548476A (en) * | 2019-09-30 | 2019-12-10 | 长春工业大学 | Preparation method and application of modified volcanic cinders filter material |
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