CN103230705A - Modified ceramic filter material and applications thereof - Google Patents

Modified ceramic filter material and applications thereof Download PDF

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Publication number
CN103230705A
CN103230705A CN2013101547548A CN201310154754A CN103230705A CN 103230705 A CN103230705 A CN 103230705A CN 2013101547548 A CN2013101547548 A CN 2013101547548A CN 201310154754 A CN201310154754 A CN 201310154754A CN 103230705 A CN103230705 A CN 103230705A
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solution
modified
filter
water
cyclodextrin
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CN2013101547548A
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CN103230705B (en
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李孟
张彦卿
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武汉理工大学
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Abstract

The invention provides a modified ceramic filter material and applications thereof. The modified ceramic filter material can be prepared by the method comprising the following steps of: (1) pre-treating a ceramic filter material; (2) preparing a modified solution, namely dissolving cyclodextrin into a dimethylformamide solvent, thereby obtaining a cyclodextrin solution; dropping isocyanate into a reaction device according to the molar ratio of 1: (7-8) of cyclodextrin to isocyanate, mixing with the cyclodextrin solution and stirring, and meanwhile carrying out ultraviolet light triggering; washing and drying a product after reaction, thereby obtaining a cyclodextrin-isocyanate copolymer; and mixing the copolymer and water, and stirring, thereby obtaining a suspension solution; and (3) taking the ceramic filter material, and then adding the suspension solution obtained in the step (2), wherein the added suspension solution can seal the ceramic filter material, then stirring, drying and roasting, thereby obtaining the modified ceramic filter material. The modified ceramic filter material obtained is simple in preparation technology, rapid in reaction, high in filter material mechanical strength, long in service life, obvious in chlorobenzene waste water treatment effect, high in practicability, and wide in prospect.

Description

Modified ceramic filtrate and application thereof

Technical field

The present invention relates to sewage treatment area, be specifically related to a kind of modified ceramic filtrate and application thereof.

Background technology

Modified filter material namely is to be coated with last layer modifier at the carrier filter material surface by physical-chemical reaction, thereby changes former filter material surface physicochemical properties, thereby improves the retaining power of filtrate, improves filtrate to the adsorption capacity of some particular matter, improves effluent quality.The modified ceramic filtrate is subjected to extensive use as modified filter material in the last few years.The research of modifier also has sizable progress, and choosing of modifier should meet easy load, do not dissolve, condition such as nontoxic.At present, modifier is of a great variety, and the preparation method is different, but still need further probe into, look for preparation simple, to organic chloride utilization absorption and the significant modifier of filter type removal effect.

Summary of the invention

The object of the present invention is to provide a kind of preparation method simple, to the significant modified ceramic filtrate of organic chloride removal effect and application thereof.

To achieve these goals, the technical solution adopted in the present invention is:

The modified ceramic filtrate is characterized in that, it can be prepared by following method:

1) preliminary treatment ceramic filter material: ceramic filter material flushing back HCl solution is soaked, and the water flushing is approaching neutral until the pH of flushing water value then, again with the ceramic filter material drying;

2) preparation modified solution: cyclodextrin is dissolved in the solvent dimethylformamide, obtains cyclodextrin solution; Described cyclodextrin solution is added in the reactor, and described reactor places 30-40 ℃ water-bath; To be 1:7-8 with isocyanates drop to mixes with cyclodextrin solution in the reactor and stir according to cyclodextrin and the mol ratio of isocyanates, carries out ultraviolet light simultaneously and cause; Wherein, the power of ultraviolet light is 2-6kw, reacts 8-15 minute; Reaction finish the back to product wash, drying, obtain cyclodextrin-isocyanates copolymer; Be that 0.1-0.15:1 mixes described copolymer with water according to described copolymer and the mass ratio of water, and stir and obtain suspension solution that the pH value of regulating described suspension solution is 6.5-7.5;

3) get the ceramic filter material of step 1) gained, add step 2 then) the suspension solution of gained, the addition of described suspension solution is as the criterion can seal ceramic filter material, stirring then, dry, roasting, sintering temperature is 450-650 ℃, and roasting time is 2h, namely obtains the modified ceramic filtrate.

In the such scheme, the particle diameter of the ceramic filter material in the described step 1) is 1.0-1.25mm.

In the such scheme, the concentration of the HCl solution in the described step 1) is 0.1-0.2mol/L, and soak time is 12-24h.

In the such scheme, the baking temperature in the described step 1) is 100-120 ℃, and be 1-2h drying time.

In the such scheme, described step 2) isocyanates in mixes the rotating speed that stirs with cyclodextrin solution be 120r/min.

In the such scheme, described isocyanates is hexamethylene diisocyanate, methyl diphenylene diisocyanate or toluene di-isocyanate(TDI).

The application of above-mentioned modified ceramic filtrate chlorobenzene in removing water.

In the such scheme, the mode that described modified ceramic filtrate is removed chlorobenzene in the water is deep-bed filtration.

In the such scheme, described modified ceramic filtrate thickness of filter bed is 150-350mm, and filtering velocity is 2-8m/h.

In the such scheme, described thickness of filter bed is 350mm, when filtering velocity is 4m/h.

Beneficial effect of the present invention is: ultraviolet light causes in the preparation process of synthetic isocyanates-cyclodextrin copolymers, under the effect of high energy ultraviolet light, reactant can be inspired active group rapidly, accelerate the carrying out of synthetic reaction, shorten the used time of conventional preparation method greatly, preparation gained copolymer is carried on the ceramic filter material surface and obtains the modified ceramic filtrate.This method gained modified ceramic process of preparing filter material is simple, and reaction speed is rapid, filtrate mechanical strength height, and long service life, practical to the chlorobenzene waste water obvious processing effect, prospect is extensive.

The specific embodiment

In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.

Embodiment 1:

Present embodiment provides a kind of modified ceramic filtrate, and it can be prepared by following method:

1) preliminary treatment ceramic filter material: be that the ceramic filter material of 1.0-1.25mm places bucket with particle diameter, rinse well repeatedly with running water, be that the HCl solution of 0.2mol/L soaks 24h with concentration, clean with distilled water flushing then, approach neutrality until the pH of flushing water value, again ceramic filter material is placed pallet to dry 2h at 120 ℃ of drying boxes;

2) preparation modified solution: at room temperature get 2.643x10 -3The mol cyclodextrin drips the DMF solvent and is stirred to cyclodextrin and all dissolves, and obtains cyclodextrin solution; Described cyclodextrin solution is added in the reactor, reactor is placed 30-40 ℃ water-bath; With 20.428x10 -3Mol high polymer monomer methyl diphenylene diisocyanate drops to and mixes with cyclodextrin solution in the reactor and stir, and carries out ultraviolet light simultaneously and causes; Wherein, the power of ultraviolet light is 4KW, and the adjustment speed of agitator is 120r/min, makes abundant haptoreaction; After the reaction, use the resulting solid product of DMF solvent wash, and use distilled water to wash again, use vacuum drying at last, obtain copolymer; Getting the 7.5g copolymer and place beaker and add 50mL distilled water, beaker is placed on the magnetic stirring apparatus to stir obtains suspension solution, is that to control the pH value of solution value be 7.5 for the NaOH of 10mol/L with concentration;

3) get the ceramic filter material of step 1) gained in beaker, add step 2 then) the suspension solution of gained, the addition of described suspension solution is as the criterion can seal ceramic filter material, stir 6h then, substance transfer in the beaker is gone into crucible, put into baking oven water evaporates is done, move into roasting in the muffle furnace then, sintering temperature is decided to be 650 ℃, and roasting time is decided to be 2h, obtains the modified ceramic filtrate.

Embodiment 2:

Present embodiment provides a kind of modified ceramic filtrate, and it can be prepared by following method:

1) preliminary treatment ceramic filter material: be that the ceramic filter material of 1.0-1.25mm places bucket with particle diameter, rinse well repeatedly with running water, be that the HCl solution of 0.1mol/L soaks 24h with concentration, clean with distilled water flushing then, approach neutrality until the pH of flushing water value, again ceramic filter material is placed pallet to dry 2h at 110 ℃ of drying boxes;

2) preparation modified solution: get step 2 among the embodiment 1) the method copolymer 5g for preparing gained places beaker and adds 50mL distilled water, beaker is placed on the magnetic stirring apparatus to stir obtains suspension solution, is that to control the pH value of solution value be 7.0 for the NaOH of 10mol/L with concentration;

3) get the ceramic filter material of step 1) gained in beaker, add step 2 then) the suspension solution of gained, the addition of described suspension solution is as the criterion can seal ceramic filter material, stir 6h then, substance transfer in the beaker is gone into crucible, put into baking oven water evaporates is done, move into roasting in the muffle furnace then, sintering temperature is decided to be 550 ℃, and roasting time is decided to be 2h, obtains the modified ceramic filtrate.

In the present embodiment, isocyanates is selected hexamethylene diisocyanate for use.

Embodiment 3:

Present embodiment provides a kind of modified ceramic filtrate, and it can be prepared by following method:

1) preliminary treatment ceramic filter material: be that the ceramic filter material of 1.0-1.25mm places bucket with particle diameter, rinse well repeatedly with running water, be that the HCl solution of 0.1mol/L soaks 24h with concentration, clean with distilled water flushing then, approach neutrality until the pH of flushing water value, again ceramic filter material is placed pallet to dry 2h at 100 ℃ of drying boxes;

2) preparation modified solution: get step 2 among the embodiment 1) the method copolymer 5g for preparing gained places beaker and adds 50mL distilled water, beaker is placed on the magnetic stirring apparatus to stir obtains suspension solution, is that to control the pH value of solution value be 6.5 for the NaOH of 10mol/L with concentration;

3) get the ceramic filter material of step 1) gained in beaker, add step 2 then) the suspension solution of gained, the addition of described suspension solution is as the criterion can seal ceramic filter material, stir 6h then, substance transfer in the beaker is gone into crucible, put into baking oven water evaporates is done, move into roasting in the muffle furnace then, sintering temperature is decided to be 450 ℃, and roasting time is decided to be 2h, obtains the modified ceramic filtrate.

In the present embodiment, isocyanates is selected toluene di-isocyanate(TDI) for use.

According to above embodiment, choose the modified ceramic filtrate for preparing under the embodiment 1-3 condition, the filtrate that obtains is used for the treatment effect that research contains chlorobenzene waste water, specifically experiment and result are as follows:

Experimental provision:

The employing diameter is 25mm, and the transparent organic glass post of high 1500mm is model filter post.Take modified ceramic particle diameter of filter medium 1.0-1.25mm, thickness of filter bed 150-350mm, filtering velocity 2-8m/h in the filter post.Adopt gravel as supporting layer, particle diameter increases gradually from top to bottom, gross thickness 100mm.

The preparation of former water: get the chlorobenzene standard specimen and be dissolved in and prepare simulated wastewater in the distilled water.

(1) processing of variable concentrations chlorobenzene waste water experiment:

Get the chlorobenzene standard specimen with distilled water be mixed with concentration be 5mg/L, 20mg/L, 50mg/L pending water sample each four parts, be numbered A, B respectively.Filtrate is the ceramic filter material before the modification in the experimental provision filter post of A water sample employing, and as a comparison case, B adopts the ceramic filter material after the embodiment of the invention 2 modifications, and thickness of filter bed is got 350mm in the experimental provision filter post, and filtering velocity is got 4m/h, and two water samples difference post is after filtration filtered.Keep the water-in and water-out stability of flow in the filtration as far as possible.

When chlorobenzene concentration was 5mg/L, chlorobenzene was removed and be the results are shown in following table 1:

Table 1

When chlorobenzene concentration was 20mg/L, chlorobenzene was removed and be the results are shown in following table 2:

Table 2

When chlorobenzene concentration was 50mg/L, chlorobenzene was removed and be the results are shown in following table 3:

Table 3

Can be drawn by above experimental result: modified ceramic filtrate of the present invention all has removal effect for the chlorobenzene waste water of variable concentrations, and effect is remarkable.Ceramic filter material clearance before modification has significantly raising, this is because be carried on copolymer-modified dose and the ceramic filter material synergy on ceramic filter material surface, ceramic filter material is because himself hole is dense, the hole tunnel is deep mixed, high porosity often is not fully utilized, do separately the time spent can not maximize the performance its adsorption effect.After the modification, copolymer-modified dose can adsorb pollutant in water fast and effectively, even the copolymer that loads in the deep hole also can make pollutant be adsorbed removal with the effect of its strong adsorption group.Simultaneously, the high porosity of ceramic filter material, high-specific surface area also provide and have stayed in the place for copolymer-modified dose, and both work in coordination with the common absorption of helping each other and remove chlorobenzene in the water.

(2) the processing experiment of chlorobenzene waste water during different thickness of filter bed:

Get the chlorobenzene standard specimen and be mixed with four parts of the pending water samples that concentration is 20mg/L with distilled water, be numbered E, F respectively, establish 3 groups of above-mentioned identical water samples for subsequent experimental.Filtrate is the ceramic filter material before the modification in the experimental provision filter post that the E water sample adopts, F adopts the ceramic filter material after the embodiment of the invention 2 modifications, thickness of filter bed is got 150mm, 250mm, 350mm respectively in the experimental provision filter post, and filtering velocity is got 4m/h, and two water samples are post filtration after filtration respectively.Keep the water-in and water-out stability of flow in the filtration as far as possible.

When thickness of filter bed was 150mm, chlorobenzene was removed and be the results are shown in following table 4:

Table 4

When thickness of filter bed was 250mm, chlorobenzene was removed and be the results are shown in following table 5:

Table 5

Thickness of filter bed is 350mm, and chlorobenzene is removed and be the results are shown in following table 6:

Table 6

Can be drawn by above experimental result: in certain thickness of filter bed scope, before the modification with modification after filtrate the removal of chlorobenzene is all had certain effect, Comparatively speaking, modified ceramic filtrate of the present invention than modification before clearance significantly improve, and along with the increase of thickness of filter bed, the chlorobenzene clearance also increases thereupon.

(3) the processing experiment of chlorobenzene waste water during different filtering velocity:

Get the chlorobenzene standard specimen and be mixed with two parts of the pending water samples that concentration is 20mg/L with distilled water, be numbered G, H respectively, establish 4 groups of above-mentioned identical water samples for subsequent experimental.Filtrate is the ceramic filter material before the modification in the experimental provision filter post that the G water sample adopts, H adopts the ceramic filter material after embodiment 2 modifications, thickness of filter bed is got 350mm in the experimental provision filter post, and filtering velocity is got 2m/h, 4m/h, 6m/h, 8m/h respectively, and two water samples are post filtration after filtration respectively.Keep the water-in and water-out stability of flow in the filtration as far as possible.

When filtering velocity was 2m/h, chlorobenzene was removed and be the results are shown in following table 7:

Table 7

When filtering velocity was 4m/h, chlorobenzene was removed and be the results are shown in following table 8:

Table 8

When filtering velocity was 6m/h, chlorobenzene was removed and be the results are shown in following table 9:

Table 9

When filtering velocity was 8m/h, chlorobenzene was removed and be the results are shown in following table 10:

Table 10

Can be drawn by above experimental result: in certain filtering velocity scope, before the modification with modification after filtrate the removal of chlorobenzene is all had certain effect, Comparatively speaking, clearance significantly improves after the modification.In addition, two kinds of filtrates are along with the increase of filtering velocity, and clearance all has reduction, but before the modification filtrate, modified ceramic filtrate clearance of the present invention reduces very unobvious.Take all factors into consideration the factor of general technical economy, can select the 4m/h filtering velocity for use in actual applications.

Choose the modified ceramic filtrate for preparing under embodiment 1 and embodiment 3 conditions, with reference to above-mentioned experiment, choosing chlorobenzene concentration is 20mg/L, and thickness of filter bed is 350mm, and filtering velocity is 4m/h, probes into the treatment effect that contains chlorobenzene waste water, and chlorobenzene is removed and be the results are shown in following table 11:

Table 11

Selected ceramic filter material is for number being 200810197939.6 according to Chinese patent application in the embodiment of the invention, the ceramic filter material that denomination of invention prepares for " utilizing the magnesium slag to prepare the method for environment friendly ceramic filtering material ".Be understandable that other commercially available ceramic filter material also can be used for the present invention.

Claims (10)

1. the modified ceramic filtrate is characterized in that, it can be prepared by following method:
1) preliminary treatment ceramic filter material: ceramic filter material flushing back HCl solution is soaked, and the water flushing is approaching neutral until the pH of flushing water value then, again with the ceramic filter material drying;
2) preparation modified solution: cyclodextrin is dissolved in the solvent dimethylformamide, obtains cyclodextrin solution; Described cyclodextrin solution is added in the reactor, and described reactor places 30-40 ℃ water-bath; To be 1:7-8 with isocyanates drop to mixes with cyclodextrin solution in the reactor and stir according to cyclodextrin and the mol ratio of isocyanates, carries out ultraviolet light simultaneously and cause; Wherein, the power of ultraviolet light is 2-6kw, reacts 8-15 minute; Reaction finish the back to product wash, drying, obtain cyclodextrin-isocyanates copolymer; Be that 0.1-0.15:1 mixes described copolymer with water according to described copolymer and the mass ratio of water, and stir and obtain suspension solution that the pH value of regulating described suspension solution is 6.5-7.5;
3) get the ceramic filter material of step 1) gained, add step 2 then) the suspension solution of gained, the addition of described suspension solution is as the criterion can seal ceramic filter material, stirring then, dry, roasting, sintering temperature is 450-650 ℃, and roasting time is 2h, namely obtains the modified ceramic filtrate.
2. modified ceramic filtrate as claimed in claim 1 is characterized in that, the particle diameter of the ceramic filter material in the described step 1) is 1.0-1.25mm.
3. modified ceramic filtrate as claimed in claim 1 is characterized in that, the concentration of the HCl solution in the described step 1) is 0.1-0.2mol/L, and soak time is 12-24h.
4. modified ceramic filtrate as claimed in claim 1 is characterized in that, the baking temperature in the described step 1) is 100-120 ℃, and be 1-2h drying time.
5. modified ceramic filtrate as claimed in claim 1 is characterized in that, described step 2) in isocyanates mix the rotating speed that stirs with cyclodextrin solution be 120r/min.
6. modified ceramic filtrate as claimed in claim 1 is characterized in that, described isocyanates is hexamethylene diisocyanate, methyl diphenylene diisocyanate or toluene di-isocyanate(TDI).
7. as the application of each described modified ceramic filtrate of claim 1-6 chlorobenzene in removing water.
8. application as claimed in claim 7 is characterized in that, the mode that described modified ceramic filtrate is removed chlorobenzene in the water is deep-bed filtration.
9. application as claimed in claim 7 is characterized in that, described modified ceramic filtrate thickness of filter bed is 150-350mm, and filtering velocity is 2-8m/h.
10. application as claimed in claim 9 is characterized in that, described thickness of filter bed is 350mm, when filtering velocity is 4m/h.
CN201310154754.8A 2013-04-28 2013-04-28 Modified ceramic filter material and applications thereof CN103230705B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106512551A (en) * 2016-12-12 2017-03-22 浙江工业大学 Amino-functionalized regenerated glass filter material for water treatment and preparation and application thereof
CN106673699A (en) * 2017-02-14 2017-05-17 福建师范大学 Preparation method of waterworks sludge-base porous ceramsite doped with bamboo powder

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CN102188952A (en) * 2011-05-12 2011-09-21 西北师范大学 Multifunctional palygorskite base adsorbing material

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CN101081343A (en) * 2007-07-04 2007-12-05 武汉理工大学 Technics of preparing sparse oil porous ceramic filtering material
CN101301548A (en) * 2008-01-25 2008-11-12 山东建筑大学 Modified filter material using zeolite as carrier and preparation thereof
CN102188952A (en) * 2011-05-12 2011-09-21 西北师范大学 Multifunctional palygorskite base adsorbing material

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106512551A (en) * 2016-12-12 2017-03-22 浙江工业大学 Amino-functionalized regenerated glass filter material for water treatment and preparation and application thereof
CN106512551B (en) * 2016-12-12 2018-09-21 浙江工业大学 For the amino functional repeat glass filtrate of water process and its preparation and application
CN106673699A (en) * 2017-02-14 2017-05-17 福建师范大学 Preparation method of waterworks sludge-base porous ceramsite doped with bamboo powder

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