CN102762295B - Composite - Google Patents

Abstract

The present invention relates to composite, relate more specifically to component based on bulk material and fibrous material and be in particular the composite adsorbing material of drinking water for purification of liquid.Mixture based on bulk material and the component of fibrous material includes the volumetric region with scalable density for the advanced composite material (ACM) of Purification by filtration liquid, these regions form the structure of material, in filter process, when liquid flows, described structure carries out self reinforcement, wherein said volumetric region constitutes the major part of this material, each region is produced with the form in crossed fiber site, these sites are combined among themselves by the fiber separated, and within described crossed fiber site and between space be filled with a kind of bulk material.

Description

Composite

Technical field

Present invention relates in general to composite, be specifically related to based on Moulded pellets component and fibrous material component for pure Change the composite adsorbing material of liquid, particularly drinking water.

Background technology

Drinking water needs to carry out after-purification in consumption location in many cases, because traditional water treatment system structure Shielding action the most always allows to remove or reduce the concentration of single pollutant until standardized quantity, and its result is that impact is drunk The quality of water.

Normally, after final drinking water, purification system is expressed as going dechlorination, organic chemicals and other pollutions The carbon column of thing.In many cases, the granulated carbon of activation is used.The advantage using the granulated carbon of described activation is that granule is lived Property carbon is a kind of cheap raw material, and this material has fairly small flowed friction and do not consolidates.One lacks Point is low adsorption rate.Therefore, when using granule activated carbon in the industry, the recommendation time of contact of adsorbent and liquid in this post Being no less than 15 minutes, this is unacceptable for living condition.Further, since absorbent particles and the freedom between them The large-size in space (space), the pillar of the graininess carbon with activation can not remove tiny contaminant particle.

As it is known, powdered activated carbon ratio granule activated carbon adsorbing contaminant quickly, but, use less grain group (granule group, part, fraction) produces high flowed friction and causes the undesirable compacting of Filter column when liquid flows (compression).In order to avoid compacting, it is usually injected into binding agent.When liquid flows, including by gathering with thermoplastic form The filter element of the active carbon particle that polymeric binder is gathered in rigid structure does not consolidates, but, in this case, because with Fixed adhesive contacts, and the adsorption volume of a part of activated carbon is not used in operation.In these filters, active carbon particle is only Occupying a part of adsorption column volume, the adsorption column volume of other parts is occupied by binding agent simultaneously.Binding agent does not adsorb pollution The activity of thing, and its introducing causes compared with the adsorption column only comprising activated carbon, and column dimension increases.It addition, manufacture this Class filter element is expensive and needs accurate temperature scenario, and the procedure parameter that other pinpoint accuracy control.

The method using activated carbon fiber in pillar is known, but these methods are fairly expensive, and works as Causing consolidated fibers during liquid flowing, this causes flow resistance to increase, although fiber compacting is significantly less than using powder activated carbon.

In the prior art it is known that mixture based on bulk material and fibrous material uses filter element to carry out liquid Body purification.For example, it is known to by a kind of absorbent, particulate material and a kind of material that can extend when it contacts with liquid The composite of composition is (in U.S. Patent Application No. 20040232068 А 1, IPC B01D disclosed in 25 days November in 2004 039/100).Adsorbing material can be such as a kind of granular activated charcoal (80-325 mesh) and granular ion exchanger resin, and Polymer stretching material can be such as based on polyacrylonitrile ion-exchange fibre.The component of described material is carefully mixed Get up and be positioned in suitable housing, this housing volume defining swell value of this stretching material.When the process that it expands In due to bulk material is fixed in stretching material when in described housing it contact with liquid time occur porous composite wood The formation of material, and also due to the inner wall pressure of this housing, with the initial component of sufficiently strong the random distribution kept together Forming a kind of structure, this composite can take this hull shape simultaneously.This stretching material can be in by weight from The quantity of 0.1% to 99.9%.

The shortcoming of described porous composite is to obtain its stage, i.e. granular particles is being fixed to extension material Time in material, it is not likely to form the most orderly cellular structure.Additionally, filter between interval in, will extend over material During material dehydration, particulate component undesirably can be moved, as a result, it is possible to there is composite porous filtering The gradually destruction of structure.

Composite is used for liquid by mixture based on granular material or fibrous material, specifically, for drinking water Another example of purification, it is Russian Federation patent number 22132729 disclosed in 10 days July in 1999, IPC B01D 039/02, and in U.S. Patent number 6299771 disclosed in November 9 calendar year 2001, IPC B01D 039/00 illustrates.

Russian Federation patent number 2132729 discloses that to include being in quantity by weight be the granulated activated of 5-30% Carbon and by weight quantity are granule and the composite adsorption material of fiber filling mixture of the activated carbon fiber form of 70-95% Material.This mixture can also be made up of ion-exchange particles and ion-exchange fibre.In composite adsorbing material, these fibers are tight Thickly fill the space between these active carbon particles.Granule and the size of fiber and relative populations are selected so that filtration Element purifies the pollutant of water quickly than the conventional filters with grain active carbon.Notable phase time between filtering Between, feature that the instruction of the filling mixture of granule and fiber improves during the interruption between filtering and absorbability extensive Multiple.

In U.S. Patent number 6299771, the filter of explanation is made up of the immixture of following component: count by weight Amount is the activated carbon fiber of 70-80% for the granular activated charcoal of 5-30% and quantity by weight.Ion-exchange particles and ion The mixture of exchange fiber can be used in filter.For granule, use and there is 50-3000 μm, preferably 100-2000 μ The granule of m size.Fibre length is 0.2-20mm, preferably 1-10mm, preferred average diameter 1-30 μm, more preferably 4-20 μm.? Grain average diameter will be greater than the average diameter of fiber.Meanwhile, in composite construction these fibers be mutually stranded in their own it Between and around closelypacked active carbon particle located adjacent one another, and there is between described granule high-grade filling Space.As a result of which it is, define numerous passages passed through for water, its cost is that filter element flowed friction is minimized. Described composite can recover characterization of adsorption (prototype) in the interval between filtering.

The examples detailed above of filter element based on composite manufacture has multiple shortcoming.As at Russian Federation patent number Disclosing in 2132729 and in the United States Patent (USP) of U.S. Patent number 6299771, the fiber of composite structure is not less Grain group (part, fraction) provide the fully fixing of grain fraction, and during water flowing is by filter element The undesirable compacting of this composite can occur, cause increase and the reduction of filter element filtering rate of filtration time, And also owing to being captured and bringing poor fixing granular particles by current, particularly powdery granule, damages composite wood Material structure, including their agglomeration, during filter element required for protection is originated, this will cause liquid purifying Poor efficiency

Summary of the invention

It is an object of the invention to produce a kind of composite allowing to avoid described shortcoming.

The technical role utilizing the present invention to realize is logical under improving the liquid purifying efficiency relevant to lead ion and chloroform Cross raising filtering rate and reduce liquid filtration time, and preserve composite structure.

The purpose of that considered and required technical role is by producing based on including having scalable density The component mixture of the granular and fibrous material of volumetric region realizes for the advanced composite material (ACM) of liquid Purification by filtration, this A little regions define a kind of material structure, and in filter process, when liquid flows, this structure carries out self reinforcement, wherein said The major part of volumetric region constituent material, forms each region having the form in twisted fibre site, and these sites are by single Only fiber is attached among themselves, and within these twisted fibre sites and between space be filled with grain Shape material.Meanwhile, the size in twisted fibre site is longer than the average length of individual fibers and not less than 1mm.If distortion fibre The size in dimension site preferably becomes 5-8mm, and the average length separating fiber is in the interval of 0.5-3.9mm, preferably 2.5- 3.5mm, and if the size in each twisted fibre site preferably become 9-16mm, then the average length separating fiber becomes 4- 15.5mm, preferably 7-8mm.For bulk material, it is possible to use granular activated charcoal, powdered activated carbon, granular ion is handed over Change resin, the particulate inorganic adsorbent manufactured based on oxide, carbonate and silicate or its any combination.With regard to fibrous material For, use has surface and can be not less than 30 М J/m², preferably not less than 60 М J/m²Polymer fiber.With regard to polymer fiber For, use fiber based on polyacrylonitrile, cellulose fibre, modified fibre based on cellulose Fypro, polyester fine Dimension, carbon fiber, the fiber comprising silicon or its any combination.Meanwhile, for being based on the polymer fiber of polyacrylonitrile, apparatus is made There are cation exchange features, anion exchange feature, ion complexation feature or described characteristic any combination of ion exchange fibre Dimension.

According to the present invention, by physics and chemical interaction between fiber attractive for prescriptive procedure by spy Levy for certain surface can and the average bulk material separating fibre length and fibrous material in composite, produce tool There is the volumetric region of regulation density.In volumetric region, between fiber, interaction energy depends on their surface energy.Fiber Should have not less than 30MJ/m², preferably not less than 60MJ/m²Surface energy.Higher fiber surface energy, can be at volumetric region The more physics of middle formation and chemical interaction point, and they higher density.When by aqueous medium according to mutual parent When the mechanism that aqueous-hydrophilic attracts realizes the physics between fiber and chemical interaction, then use have surface can < 30MJ/m²Fiber time, these fibers be not enough to formed low-density volumetric region degree under can assist with water and each other Make.Therefore, the surface of fiber can define the density of volumetric region.The regulation of volumetric region density can change filtering rate: Filtering rate can increase, and filtration time will reduce accordingly.

According to the present invention, complete each region with the form in crossed fiber site, and bulk material is distributed in described In crossed fiber site, and it is distributed there between with lower degree.Bulk material is maintained at knot by the fiber site interweaved In structure and not allowing granule move and compress, the fiber interweaving simultaneously separated in composite construction is forming consistent (in conjunction with) Described in the cumulative volume of the composite of structural matrix around site.The size in most crossed fiber sites can be more than separating fibre The average length of dimension.Separate fiber formation and there is more low-density structural region.Due to the relatively low-density of structural region, intertexture Fiber site relative to each other can move under the effect of external mechanical force, meanwhile, there is not the layering of composite, I.e. before liquid filters, composite moves freely in the dry state, and this allows easily to fill up with its necessary amount or fill out Fill the post of what desired Filter column or unit.In filter process, liquid crossed fiber site both sides and around mobile.Logical Crossing this liquid filtering rate to increase, crossed fiber site provides the flow resistance of reduction.

According to the present invention, the size in each crossed fiber site is not less than 1mm.If separate fiber average length be from 0.5mm to 3.9mm, preferably 3-3.5mm, the most each crossed fiber site is preferably dimensioned to be 5-8mm.If separating fiber Average length is from 4mm to 15.5mm, preferably 7-8mm, and the most each crossed fiber site is preferably dimensioned to be 9-16mm.Make With when there is average length more than the fiber of 15.5mm, these fibers start cooperate with their own consumingly formed multiple rings and Knot, these rings and knot disturb the formation of this composite structure, and the major part of this composite structure is made up of volumetric region 's.

In more detail, by separating the physics of fiber and/or physics and the interaction of chemistry, these fiber positions interweaved Point is connected to each other.By these fibre machineries are bonded to each other and realize Physical interaction.When fiber contacts with water, physics Appearance is started with chemical interaction.In liquid flow process, the quantity of physics and chemical interaction point increases.These point The most, volumetric region density increased even more.In the case of increasing density, add volumetric region and keep the energy of bulk material Power.Physical interaction also appears in the point under the liquid stream effect being in filtration.There is fiber in this way each other another Outer mechanical bond, i.e. at the end of filtering and after drying, composite do not shrinks, be not compacted or its structure It is not destroyed.Owing to strengthening the structure of composite, it can take to accommodate the shape of its any situation, simultaneously from this In situation, the form of single type integrated element can easily be taked by this composite (under not having deployment conditions).At liquid stream With in the case of " self strengthen " during Dong, this composite running through filter element required for protection source keeps it to tie Structure.

In the prior art it is known that use the powdery granule of bulk material.It is known that with based on coarse part The filtering material of activated carbon compares, the absorption surface expanded due to powder particle, granule group (part) carbon the filtration manufactured Material absorption pollutant are more preferable.But, normally, obtain filtering material different phase, under agitation, also it When using granular activated charcoal between granule, powder partial particulate is easily connected to each other and easily fills free space.This causes Producing bigger aggregation and the overcompaction of filtration of granule group (part) granule, this overcompaction substantially increases Add the flow resistance of filter element and reduce purification efficiency.According to the present invention, granule group (part) distribution of particles is in intertexture In fiber site, and it is distributed there between with lower degree.By its compact texture, these fiber sites interweaved are protected Hold powder particle and do not allow them move and assemble.What major part powdered ingredients was used in composite by this offer can Energy property, this part allows to reach to remove lead ion and the usefulness of chloroform from liquid together with other components of this composite (efficiency).

Composite according to the present invention represents a kind of mixture of bulk material and fibrous material.

For bulk material, using such as a kind of granular activated charcoal, powdered activated carbon is (by Filipine Davao Chemical produces；Or Sri Lankan Bieco-link Carbons (PTE) LTD produces), granular ion exchanger resin (С 243, U.S. Sybron Chemicals Inc. produce), particulate inorganic adsorbent based on oxide (Russia " HromLab " company, 0.05-0.1mm), particulate inorganic adsorbent based on carbonate (" Kamnizdes " company of Russia, in vain Marble 0.1-1mm) and particulate inorganic adsorbent based on silicate (Russia VOSTOK-ENERGO JSC, 0.1- 0.9mm), or their any combination.

For fibrous material, (" Polymarct " company of Russia, has 34MJ/m to use cellulose fibre²Surface Can), modified fibre based on cellulose (Russia " DKM Venture projects " company, 43MJ/m²), polyamide fine Dimension, polyester fiber (Russia DonPolymerMarket JSC, 31MJ/m²), carbon fiber (Taiwan К oTHmex, 47MJ/m²), Silica fibre (U.S., Dowex, 36MJ/m²), polymer fiber based on polyacrylonitrile.The polymer being based on polyacrylonitrile is fine For dimension, it is any combination of that use has cation exchange properties, anion exchange properties, ion complexation characteristic or described characteristic Fiber (such as, is studied the fiber Copan, 70MJ/m produced with production company by Russia " TES "²).

For example, it is possible to according to including that two stage following method obtains this composite.

In the first stage, according to the present invention, the pre-cut fiber of a certain length is exposed to pretreatment.Fiber is added It is downloaded in a tank thus is such as stirred by centrifugal water pump, be then based on the fiber 1m for 10-15kg³Add Water.After this process terminates, by draining pump (wet pit pump), final material is unloaded in centrifuge.In order to prevent Loss of product, is arranged on specific sieve mesh bag in centrifuge.Centrifugal process preferably runs 7 minutes.Then unload from centrifuge Carry the fiber in sieve mesh bag.Then it is dried.The institute processed in steps in, owing to producing with the form in crossed fiber site These volumetric regions, it is provided that the strong agitation of fiber.

Second stage initiates to prepare fibrous suspension.For this purpose it is proposed, feed water in this tank and load pre-simultaneously The fiber first processed.Based on the loading mixture 1m for 100-180kg³Water use water.Under vigorous stirring at this tank Middle prepare fiber unit for uniform suspension in water.Then by pump, the suspension pump of acquisition is delivered to the group for this composite Divide in the tank of mixture, under this suspension of continuous stirring, wherein load a kind of bulk material.If this bulk material is by these The combination composition of component, the most as one man performs the loading of every kind of Granular compositions.In 1-15 minute under the water speed of 1-2m/s Perform suspension by centrifugal water pump to stir.At the end of whipping process, it is unloaded in centrifuge be used for by the mixture of preparation Water is removed from mixture.In order to prevent loss of product and contribute to the mixture of unloading preparation, will there is the specific of sieve mesh bag Container is arranged in this centrifuge.The speed of rotation set with centrifugal drum during the setting time (depends on adsorbing mixture Content) perform centrifugal process.Obtain composite institute in steps in, the initial component of strong agitation promotes initial group continuously The formation of separation structure, these simultaneously including that the bulk material of powdered activated carbon is filled in that the first stage produces in advance interweave Fiber site.Define and be filled with bulk material and be in the structure with volumetric region of crossed fiber site form.

The composite obtained in this way is poured in suitable adsorption column, concentrates and load.

Detailed description of the invention

Confirm to utilize the aspect can as the industry of lead ion and chloroform using this kind of indicant in invention by example below Application and the probability realizing liquid purifying efficiency are real.

Embodiment A(is according to the present invention)

In order to prepare Filter column based on composite, use following components: based on polyacrylonitrile, there is average length 3.5mm, surface energy 50 М J/m²Cation exchange fibre " Aqualen 2 " (by Russia " Kemetsorb " company produce)； 20x50 mesh, the granular activated charcoal (being produced by Philippine " PJAC ") of 250-280 micron；50x200 mesh, the powder of 50-250 micron Shape activated carbon (is produced by Philippine " PJAC ")；Grade be 0.2-0.6mm cation exchange resin Lewatit CNP LF(by Germany LanXess produces).The composite obtained in this way is loaded into (polypropylene, diameter in cylindrical adsorption post 60mm, high 70mm).Therefore, 3 posts it are made for: A1, A2, A3(table 1).In filter process, it is vertically mounted post A, by liquid Pumping is passed through from top to bottom.

Comparing embodiment B(is according to prototype)

To have average length 10mm by weight, surface can 50MJ/m²The activated carbon " Aqualen " of 1 part of cutting fine Dimension (being produced by " Kemetsorb " company of Russia) is placed in container, and adds the water of 100 parts by weight thus make one Plant suspension.7 parts are had the granular activated charcoal F200(U.S. Calgon that average rank is 20x50 mesh, 250-850 micron) add It is added in suspension and mixes the most well.The mixture centrifugal drying of generation is separated and is used for reducing water content Until by weight less than 40%.Then the dehydrating mixt of adsorbent is densely loaded in cylindrical Filter column.Therefore, 3 posts are manufactured: B1, B2, B3.In filter process, it is vertically mounted post B, and liquid is pumped across under upper post B (table 1).

Table 1. adsorbs the weight (g) of component in filter cylinder

In all cases, the cumulative volume of pillar has been completely filled with composite.

Embodiment 1

The lead ion standard test solution making concentration be 0.15mg/l by gravity from top storage tank by adsorption column A1, A2、A3、B1、B2、B3.Fixing filtration time, and limit plumbum ion concentration in the water of filtration.According to GOST 1829372 " drink By water, the method determining lead, zinc, silver content " defined plumbum ion concentration in drainage (table 4).

Similarly, the chloroform standard test solution making concentration be 0.5mg/l by gravity passes through adsorption column from top storage tank A1、A2、A3、B1、B2、B3.Fixing filtration time, and limited the chloroform concentration in drainage.According to MUK 4.1.646-96 " gas chromatography determines the method explanation containing halogen species in water " defined the concentration of chloroform in drainage.Result is in table 2.

Table 2. is removed lead ion and removes chloroform

The % of *-removal

This table shows in the case of filtering rate increases, and 1 liter of standard test solution is little by the filtration time of a series of post A In the same standard test solution filtration time by a series of post B.It addition, different from prototype, wherein filtering mixt Do not allow purification and realize about the gratifying figure of lead ion and chloroform, due to its structure, the composite of proposition (as shown in table 2) allows to reach the effective purification about described parameter.

When the most favorably combining when the present invention is described with preferred embodiment with being presently considered to be, it is necessary to It is understood by the present invention not limited by described embodiment, on the contrary, it covers the design in the serial claim proposed Different update in limiting with scope and variant.

Claims (11)

1. mixture based on bulk material and the component of fibrous material is for a composite for Purification by filtration liquid, and it is special Levying and be, described composite includes that forming described composite structure has the volumetric region of scalable density, filtered In journey, when liquid flows, described structure carries out self reinforcement, and wherein said volumetric region represents the maximum portion of described composite Point, producing each region with the form in crossed fiber site, these sites are tied mutually by the fiber separated Close, and within described crossed fiber site and between space be filled with bulk material, described crossed fiber site is Most size is more than the average length of separation fiber, and described fibrous material is to have not less than 30 М J/m²Surface can Polymer fiber, the size in each crossed fiber site is not less than 1mm, and the average length separating fiber is from 4mm to 15.5mm.

Composite the most according to claim 1, it is characterised in that the size in each crossed fiber site is 5-8mm.

Composite the most according to claim 1, it is characterised in that the size in each crossed fiber site is 9-16mm.

Composite the most according to claim 1, it is characterised in that the average length separating fiber is 7-8mm.

Composite the most according to claim 1, it is characterised in that described bulk material is granular activated charcoal, granular from Sub-exchange resin, particulate inorganic adsorbent based on oxide, carbonate or silicate, or their any combination.

Composite the most according to claim 1, it is characterised in that described bulk material is powdered activated carbon.

Composite the most according to claim 1, it is characterised in that described fibrous material is to have not less than 60 М J/m² Surface can polymer fiber.

Composite the most according to claim 1, it is characterised in that described polymer fiber is fibre based on polyacrylonitrile Dimension, cellulose fibre, modified fibre based on cellulose, Fypro, polyester fiber, carbon fiber, comprise silicon fiber or Their any combination.

Composite the most according to claim 7, it is characterised in that described polymer fiber is fibre based on polyacrylonitrile Dimension, cellulose fibre, modified fibre based on cellulose, Fypro, polyester fiber, carbon fiber, comprise silicon fiber or Their any combination.

Composite the most according to claim 8, it is characterised in that described polymer fiber based on polyacrylonitrile is There is any combination of ion exchange of cation exchange features, anion exchange feature, ion complexation feature or described feature Fiber.

11. composites according to claim 9, it is characterised in that described polymer fiber based on polyacrylonitrile is There is any combination of ion exchange of cation exchange features, anion exchange feature, ion complexation feature or described feature Fiber.