CN1051681A - The sclerosis glued membrane of Xing Chenging on the spot - Google Patents

Abstract

The stable asccharin glued membrane that forms on the spot on porous carrier, the polyvalent cation of this film through making equivalent at least contacts and modification with anionic group in glue.

Description

The sclerosis glued membrane of Xing Chenging on the spot

The present invention relates on porous carrier the stable asccharin glued membrane that forms on the spot, this film is through contacting and modification with multivalent metal cation.

No matter be used for (particulate) microfiltration, ultrafiltration or counter-infiltration, forming film on the spot all has many attractive features in isolated by filtration.Under the strict demand that the chemical corrosivity that satisfies by temperature and feed produces, the range of choice of substance classes that can form film is very wide.A key character is, owing to pollute or other is former thereby when degenerating, they can be removed on the spot and change when the performance of film.

To some purposes, the present film of formation on the spot has various defectives, as based on hydration Zr(IV) film of oxide is shown.Remove and change these films and need several hours.This is inessential, if film properties all was satisfied with in several weeks.But if must under situation about changing during a day or several days, upgrade faster if not must also wishing very much.

Be used for food and bioprocess technology class hour, wish that also membrane material is nontoxic usually, preferably belong to material that generally believes safety (GRAS) or the material that is used for food by food and drug control department (Food and Drug Administration) approval.Like this, product may be polluted just unimportant by membrane substance.

An interested herein class film forms additive and comprises asccharin glue, as alginic acid salt, xanthic acid salt, pectin class, carrageenan class (Carrageenans), guar gum, carboxymethyl cellulose and hard dextran class.Wherein manyly be approved for food in commercially availabie kind.In general, wish that they form the good film of hyperfiltration performance easily, and in some cases, formation can be filtered the film of most of dissolving salt.As report: the J.T.McKinnon of the visible U.S. environment protection of example mechanism (U.S.Environmental pro-tection Agency), EPA-600/2-79-209(1979) with alginic acid salt and xanthic acid salt.

United States Patent (USP) 4,851,120 have described use polysaccharide and derivative thereof as composite membrane rather than carry out dividing dried up as forming film on the spot from organic matter.The water solubility that it recognizes the people and uses the polyvalent cation material can make film reduces.

These glued membranes can be removed in purifying (CIP) solution at an easy rate through being exposed on the spot, and as hypochlorite or alkaline peroxide, these are usually used in purification and the sterilization of every day in the food processing apparatus.They can only increase a bit than the normal clarification time being less than formation in 30 minutes basically.

Because through GRAS approval and have above-mentioned feature, form glued membrane on the spot to being used for as at United States Patent (USP) 4, slurries (Ultrapress) are pushed or purify to the usefulness of describing in 716,044 " the super extruding ", and many other food technologies will be selectivity likely.But we some difficulty occurred when forming glued membrane on the spot and estimate.

With regard to the film that forms down in low pressure [pressure is up to about 50 gauge pressures (psig)], separating property is instability owing to depend on factor except the granularity of the aperture of film and separated material.For example, find to depend on pH and excess salt concentration at the mosanom film elimination bovine serum albumin (BSA) in the presence of filter aid that forms on the spot on the sintered stainless steel tube for about 0.05 to 0.15 micron with the aperture.Near the equipotential point of BSA or when electric charge during by the excess salt shielding added, species (molecular weight about 69,000) can penetrate film greatly, and when keeping clear of isopotential point when not having excess salt, these big species are removed at pH.Therefore realize separating with the mosanom film that under low pressure forms and to depend on Coulomb effect to a great extent.

The film of film as describing in the report of above-mentioned McKinnon that employing forms down at high pressure (greater than 50psig, more preferably greater than 150psig) according to particle diameter, separates better.But these films are unsettled, especially operate as increasing under flow or the condition in pasteurization at a variety of causes, under desirable high temperature (greater than about 45 ℃).Instability be meant glued membrane promptly by produce material from matrix remove and can not produce economically with practicality on interest.Even find also that at room temperature unsettled glue can be changed from forming film on the spot when when containing coarse grained feed and contact.Therefore, they are wishing that film has in the application of longer life and do not have attraction especially.

We have found a kind of method of improving glue film performance, be provided to be shaped as have under the pressure bigger according to particle size separation ability and can under wideer condition and range, form more stabilising membrane.

Glue of the present invention is to have anionic group such as metal carboxylate or Sulfates natively attached to the glue on the polymer, or has the glue of these negative electrical charge groups through chemical modification.This method makes film contact with polyvalent cation after being included in formation, perhaps preferably forms film in the presence of polyvalent cation.Cation Ca(II) and the Mg(II) because low-cost and hypotoxicity thereby be best.Preferably chelating agent such as citric acid are joined in the formation solution that contains natural gum and polyvalent cation.

The film that forms on the spot of the present invention is through the asccharin glue that has an ionogen of negative electrical charge being exposed in the solution that contains polyvalent cation and the continuous film that forms, cationic equivalent equals the molal quantity of the ionogen that exists in (better be at least more than 0.001 mole, be more preferably at least more than 0.0025 mole) glue at least in contact solution.Be preferably, forming in the solution glue is closely contacted with polyvalent cation forming film, particularly when the aperture of matrix during greater than about 0.05 micron.

Best asccharin glue is selected from alginic acid salt, xanthic acid salt, pectin class, carrageenan class, the set that the guar gum that has anionic group of being modified, carboxymethyl cellulose and scleroglucan class are formed.Those natural gum of equivalent weight minimum preferably, just per unit mass has the resin of maximum anion ionogens.Best natural gum is the alginic acid salt.

The polyvalent cation species can be that any known polyvalent cation that provides under contact conditions is the electric charge cationic species of 2+ at least.Being preferably provides the Ca(II) and the Mg(II) the polyvalent cation species, especially use in the food applications of the material of GRAS approval in hope.Be preferably, the counter ion counterionsl gegenions in the species also are acceptable in food applications.Therefore, calcium carbonate is to introduce the Ca(II) compound of species the best.

Porous carrier can be any carrier that is used to support to form on the spot film known in the art.Be preferably Lacunaris metal carrier, it can not corroded by the fluid that will use therewith and can be cleaned and do not damaged by CIP solution.Preferably austenitic stainless steel, the especially austenitic stainless steel of 300 types, the particularly austenitic stainless steel of 316L type.These carriers generally are by about 30 to the 100 microns non-sphere of granularity, and are erose granuloplastic.The aperture is about 0.5 to 10, and better is 0.5 to 5 micron, and the about 5-20% of the porosity of carrier.

Optimum carrier is above-mentionedly to list for reference at this at U.S. Patent application No.07/310141() stainless steel carrier of the change described.This optimum carrier (change matrix) is a kind of by diameter 30-100 micron, the aperture is the granuloplastic porous metals matrix of 0.5-10 micron, and the hole of a side of matrix is by the degree of depth of the sintered metal oxide powder filling of 0.2 to 1.0 micron of diameter to the 30-100 micron.The best metal oxide powder is the titanium dioxide that is the rutile crystal form.

The aperture of porous matrix should be enough little so that form continuous film.Being preferably the aperture is 0.05 to 0.5 micron, and better is 0.05 to 0.1 micron.Be preferably, if the aperture greater than 1 micron such as not changing in the matrix above-mentioned, should add a kind ofly as at United States Patent (USP) 3,577,339(lists for reference at this) in the filter aid described form film on the spot with help the bridge in the matrix connect so that form continuous film.For changing matrix, filter aid is not best but can uses.

Film of the present invention can at first flow through in the known mode of this area professional, walk around and contact porous matrix and form, so that make continuous film such as the asccharin glue of metal carboxylate or Sulfates or the asccharin glue that had these negative electrical charge groups by chemical modification with the anionic group that has natively that is connected on the polymer.Then the continuous film shape of gained being formed film on the spot contacts with polyvalent cation.In order to form continuous film with unmodified glue, the aperture of porous matrix must be enough little, otherwise must use sufficient filter aid with the bridge joint of realizing the hole and must use stricter formation condition (as form pressure enough height so that flow greater than 100gfd)

Yet preferably, film of the present invention at first through a kind of fluid preferably in the water preparation glue form with the enough cationic solution of multivalence, and solution is being contacted so that make a part of fluid pass matrix under enough pressure with stromal surface.The pressure that uses depends on the hyperfiltration purposes.If use under the condition that can form continuous film, higher pressure helps to form film, the i.e. lower film of permeability more closely.Other forms parameter and circulation rate, the additive capacity that per unit area forms film with and concentration, flow rate and temperature can influence the character of film, this is known in the art.

Method with the application can under low pressure form continuous film, even be that not use filter aid on 0.05 to 0.3 micron the not change matrix also be like this in the aperture.Do not change the present invention, need higher pressure to make continuous film.Therefore, it is bigger to form the scope of film in this method on the spot.Under low pressure the film of Xing Chenging is when in the Ca(II) in the presence of character also can to take place when forming change.In fact, the alginates film of observing elimination BSA can not form on greater than 1 micron whole unaltered matrix in the hole at all, yet through adding the Ca(II), keep clear of the BSA isopotential point and do not having the alginates film that can form complete energy elimination BSA under the interpolation salt situation.

To many purposes, optimum pressure is low when forming glued membrane, for about 15 to 50psig.Under low pressure the water permeability of the film that forms from the alginic acid salt according to method modification of the present invention is about every gauge pressure of every square feet of film 1 to 2 gallon of every day (gfd/psi), and is not about 2-5gfd/psi according to the alginates film of method modification of the present invention.

Although upper limit of pressure finally determines that by the intensity of matrix best high pressure can be determined according to the compactness of the film of hope by one of skill in the art.High pressure (is higher than 50psig, especially 150-300psig) will form closely film and extra-high voltage (approximately 950psig) will form tightr film (0.1-0.2gfd/psi), even under situation not, also be like this according to the alginic acid salt of method modification of the present invention.Form if (comprise pressure) under the same conditions, generally tightr according to the film of modification of the present invention than unmodified film.

Formation solution should mix fully and is even so that form the film of formation on the spot of continuous film shape effectively.Can regulate temperature and pH so that form a kind of so uniform formation solution.

High temperature can increase solubility.Can use higher temperature if when forming, have polyvalent cation when not existing.Be preferably about 5 °-50 ℃ of formation temperature.PH should be enough to guarantee to form homogeneous solution.If pH is too low or too high, precipitation or cation just may take place replaced.Be preferably pH in the 3-8 scope.On request by add a kind of inorganic acid or organic acid preferably through the GRAS approval such as the lemon acid for adjusting pH.Citric acid is as a kind of chelating agent significantly, and is best when being used to form before the film when glue and polyvalent cation species are mixed in fluid.

The polyvalent cation amount should provide the suitable cation of anionic group, preferably Ca(II in an amount of at least and the film) or the Mg(II).Be preferably, cation should surpass this stoichiometric amount.Goodly be, this is excessive in 0.001 mole, and the best is greater than 0.0025 mole.

Asccharin glue answers capacity to form continuous film on porous matrix in the formation solution.As for the change matrix in most of purposes, every square centimeter of normally better scope of about 0.1-1mg.The concentration that forms glue in the solution depends on the glue of use, but should be about 5-300 mg/litre (mg/l).

Forming solution circulation rate and time should be enough to generate and have for using the continuous film of desirable permeability.Too high permeability also may be represented to form poor film (discontinuous), obtains insufficient separation.In these cases, through reducing the permeability that circulation rate can obtain to require.This area professional can determine that iptimum speed under setting pressure and time are normally to form film.

Film forms and can measure through observing flow.When film formed, flow can descend under setting pressure.Best, form film by increasing pressure, in increasing pressure, flow reduces, until pressure up to making film form desirable tight ness rating.

When forming glued membrane, the ratio of circulation rate and flow by film can be used for the permeability (flow of unit are unit pressure) that obtains to wish.For example, at pressure 255psig, circulation rate 13 feet per seconds, reaching minimum flow in the formation of program similar to Example 4 is 147gfd, corresponding permeability is that 0.27gfd/psi(is adjusted to 37 ℃).Through speed being reduced to 6 feet per seconds, under 230psig, can obtain the flow of 67gfd, corresponding permeability is 0.12gfd/psi, adjusts to 37 ℃.

Embodiment 1

Formed three mosanom films on porous stainless steel matrix, the surface of this matrix is changed, so that its surface has littler aperture, and as U.S. Patent application No, (the change matrix) described in 07/310141.Matrix is long 10 feet by four, and the pipe of 1.25 inches of internal diameters (1.25 " id) is formed its total surface area about 13 square feet (sq.ft).

Feed contains 88 liters of deionizations (counter-infiltration) water, respectively wherein:

-to film 1, do not add calcium compound or citric acid;

-to film 2, add capacity calcium carbonate and make solution contain about 0.0025 mole of (M) Ca(II) and add the capacity citric acid and obtain 0.0055M, final pH about 3.6;

-to film 3, add capacity calcium nitrate and obtain the 0.0025MCa(II) and add the capacity citric acid and make pH reach 3.5.

The dispersion that also adds 0.3 micron particles and 0.65 0.014 micron particles that restrains of 0.65 gram.In each forms liquid, add the capacity mosanom and make per square inch that the film surface is 1 gram, feed concentration is every liter of 0.00078 equivalent.

The 4th film at single test section in 0.0025M Mg(II) in the presence of form, Mg is with (MgCO ₃) ₄Mg(OH) ₂5H ₂O adds; And add every square feet of film surface of equivalent alginates, but the concentration in the solution is slightly different: 0.00043N mosanom and 0.0018M stoichiometric amount citric acid, this is to obtain final pH 3.5 necessary concentration.

Solution circulated about 18 minutes under about 12 feet per seconds in each case.Afterwards, forcing an especially big sponge ball by this system, collect the liquid that extrudes, simple alginates and Ca(II) its volume of situation is 20 liters, to the Mg(II) situation is 5 liters.

Under the situation of the film that no divalent ion forms, solution colour is a grey.When adding divalent ion, solution is transparent, and the turbidity that records through 90 degree scatterings in the Brice-Phoenix light scattering photometer sees Table 1.

Table 1

Film exposes turbidity

1 no divalent ion 0.217

2 Ca(II), citric acid 0.023

3 Ca(II), no citric acid 0.005

4 Mg(II), citric acid 0.027

The film that no divalent ion forms is from managing the degree of replacing significantly than in the Ca(II) or the Mg(II) in the presence of the film for preparing bigger.

The mosanom film that another forms under similar fashion is exposed to the 0.0025MCa(II subsequently), in the citric acid solution of pH3.5.The solution turbidity that sponge ball extrudes is 0.105.Be exposed to subsequently and improved stability in the divalent ion, but do not reach the degree that ion exists formation down to be reached.

Embodiment 2

The alginates film is 5/8 " i.d. changes on the matrix porous stainless steel (about 0.05 micron of aperture), 30 ℃ of temperature, circulation rate 6 feet per seconds form at 25psig from the solution that contains the 0.00065M mosanom.Adding calcium nitrate under a kind of situation and make the Ca(II) concentration reaches 0.004M.Do not add the Ca(II under the another kind of situation).Measure then these two kinds of films add with not with under the salt during at pH8, the functional relation of elimination bovine serum albumin (BSA) and circulation rate.The results are shown in table 2.

Table 2

The elimination of circulation rate KCl addition

Meter per second mol Ca(II) exposes

Do not expose

0.4 0 0.4 0.98

0.8 0 0.95 0.98

1.0 0 0.98 0.95

0.2 0.01 0.40 0.80

0.8 0.01 0.40 0.95

1.0 0.01 0.45 0.95

This embodiment shows that under low pressure the alginates film of Xing Chenging can pass through a large amount of HMW species from some liquid composite, and is exposed to and makes it to change under these conditions more effective milipore filter in the bivalent cation.It shows, no Ca(II) time, in the hole at carrier-feed interface, only apply alginates, the result, elimination mechanism is mainly ion exclusion, and this is common at amberplex.The Ca(II is arranged) time, glue forms continuous film.Adding the salt amount when being zero, the effective charge on the BSA is quite high, is existed much bigger down by the elimination amount of exposed film not than salt with the variation and the corresponding concentration polarization of circulation rate.These difference have confirmed that the not elimination of exposed film mainly is owing to Coulomb effect, and exposed film mainly is because steric effect.

Embodiment 3

To a series of alginates films of having been stablized by divalent ion be recycled to 80 ℃ and when returning 55 ℃ the water changes in permeability during at about 55 ℃ compare.Membrane carrier is that membrane area is 3.25 square feet of internal diameter 1.25 " id porous stainless steels.At first make the feed solution of about 200 liters of deionized waters pH reach 3.5 through adding citric acid.Add calcium carbonate and magnesium carbonate then, and the pH that makes of adding weighing gets back to 3.5 citric acid.In all cases, citric acid molal quantity and divalent ion (Ca(II)+Mg(II)) ratio of molal quantity is about 3-3.5.Every square feet of film is added the about 0.3 micron filter aid of about 5mg granularity and about about 0.014 micron filter aid of 5mg granularity.The capacity solution of sodium alginate that adds 100 milligrams every square feet (mg/sq.ft.) then; The about 0.0000085 equivalent carboxylate of feed concentration/liter.Along with flow reduces step by step the pressure of the film of circulation formation solution is increased to about 300psig, about 50 ℃ of temperature then).

Form identical Mg(II) concentration (approximately 0.001M) but the film of Different Ca (II) concentration.Test section links to each other successively and ° is returning the temperature scanning that carries out the water permeability under 50 ℃ from room temperature to 80 again.As the results are shown in the table 3 of divalent ion concentration function.Relatively be according to functional relationship of temperature being carried out the about 55 ℃ permeabilities (gfd/psi) that record and be adjusted to 37 ℃ when temperature rises and descend by the known water permeability.The about 200psig of pressure.Thereby the film through there being a different step to form with no bivalent cation is produced different slightly permeabilities also to be included in and wherein to carry out hysteresis relatively.

Table 3

Cation total mole number permeability (gfd/psi)

(mol) M(II)/equivalent

The Ca(II) Mg(II) alginates ascending temperature decline temperature

0 0 0 0.46 0.65

0.0003 0.001 164 0.94 1.35

0.0006 0.001 200 0.86 1.00

0.0024 0.001 411 0.86 0.94

Be recycled to the unstability that the increase of permeability behind the higher temperature shows film.Can see that being exposed to divalent ion has reduced this unstability.

Embodiment 4

This embodiment shows the Ca(II) concentration just formed the back in the influence of the about 40 ℃ water permeabilities that record to the alginates film at film.Film is the general step formation used in embodiment 1 and previous embodiment at about 200psig.Condition as far as possible unanimity-formation time 17 to 21 minutes and when forming maximum temperature between 52 ° to 60 ℃.Except indicating in the table 4, calcium adds with calcium carbonate, and makes citric acid reach itself dissolving and adjusting pH.

Table 4

The Ca(II) mosanom citric acid permeability

Molar concentration equivalent/rise molar concentration pH gfd/psig

（37℃）

0 0.00015 0.00075 3.5 2.01

0 0.00078 0.00074 3.5 0.97

0.0013 0.00078 0.0028 3.5 0.79

0.0026 0.00015 0.0055 3.5 0.72

0.0026 0.00078 0.0066 3.5 0.65

0.0026＊ 0.00078 0 3.5 0.54

0.0026＊ 0.00078 0 6.6 0.38

0.0079 0.00078 0.0165 3.5 0.15

* Ca(II) add with nitrate, pH regulates with nitric acid.

Can see the permeability reduction of film when calcium increases.Although after temperature scanning, measure flow the II along with Ca(is also arranged) increase and downward trend has the more hysteresis than a last embodiment.General this is because the ratio of bivalent cation and the equivalent of alginates is significantly smaller than the situation of using low concentration of alginate-be 0-17.3 here in the present embodiment, is 0-400 and hang down concentration of alginate.Confirmed that using " super extruding " method to produce pineapple timing condition used herein from skin be good.

With similar approach in 0.0026M Mg(II) (pH3.5) there are the permeability about 1.4 of the film that forms down in 0.00043N alginates, 0.0053M citric acid.

Embodiment 5

Contain four 1.25 and " on change matrix porous stainless steel, forming film in the experimental provision of id pipe.Add 14.8 kilograms of citric acids in 265 liters of filtered water, pH is 2.5 like this.Add then calcium carbonate make reach 0.0025M Ca(II).Mosanom 0.1g/sqft is added that capacity filter aid 0.01g/sqft is mixed together into a kind of water slurry and adds then.Feed in about 40 ℃ of circulations until the permeability that reaches 1.87gfd/psig at 300psig (1.66 are adjusted to 37 °).Drain forming solution, the permeability that water records is adjusted to 37 ℃ and is 1.52gfd/psi.

Add muddiness then and take off pectin (depectinized) cider, it is generally processed with diatomite filtration.In pressure scanning, obtain the flow of 280gfd at 244psig.In the test of 200psig, flow drops between 220 to 300gfd usually subsequently.(permeate) is transparent for penetrating fluid, general about 0.5NTU, and sugared throughput surpasses 98%.

In this purposes, require high flow capacity and use every square feet of the low mosanom of measuring.When the purification pear juice, obtained similar result.

Embodiment 6

" super extruding (ultrapress) " means and not only pushes juice but also purify simultaneously from fruit.In this case, feed material is a pineapple juice, for canned pineapple wishes to extract juice from its skin.Experimental provision contains 480 feet about 3, and " porous stainless steel of id, its film surface is 360sqft approximately.From about 1900 premium on currency, form film, to wherein having added 2500 gram lemon acids, and added calcium carbonate and make pH reach 3.5.Along with the filter aid that uses in other embodiments adds 1 gram alginates/sqft; It is desirable to lower initial permeability.In 8-15 hour experimentalists and technicians, a wheat harvesting period has been carried out in experiment, and range of flow is 20-40gfd, the about 600psig of inlet pressure in the operation and outlet pressure is changed to 100-300psig.Product is transparent, and the recovery of by volume penetrating fluid is approximately the 60-75% of feed.The sugar throughput surpasses 80%.Operating temperature is basically between 55 °-75 °.In this case, not only comprise change matrix but also comprise conventional pipe.In general, initial performance is similar, is easier to cleaning but change matrix, therefore has more uniform performance.

Embodiment 7

The step that employing is similar to embodiment 1 film 2 forms the alginates film.Carrier is four 5/8 that are arranged in parallel, and " id porous stainless steel assembly, total membrane area are 6.3sqft., to comparing from the performance of the plain boiled water of pulp mill and the performance of blank pipe assembly they are linked to each other successively wherein, pressure scanning is for to return 115 again from about 30-220psig.Although it is high by 35% that the permeability ratio of blank pipe under initial pressure has the pipe of film.But at the second place (70psig), the pipe permeability that has film is high by 25%.When returning 115psi, the flow of the pipe by having film is 250gfd, compare with it what pass through blank pipe is 103.The feed circulation rate is 15 feet per seconds in this experiment, about 50 ℃ of the temperature of processing stream.The separation of two test sections is all good, essentially no suspended solid in penetrating fluid.This test operation has carried out two hours.

Film is removed, changed, and to plain boiled water experiment 8 days.Pressure changes between about 60 to 110psig during this, is 200gfd when flow begins and is 90gfd when finishing.

Claims (17)

1, a kind of method that on porous matrix, contains the formation ultrafiltration apparatus that forms film on the spot, this method comprises makes a kind of flow of solution mistake that contains the asccharin glue of anion ionogen in fluid, walk around and contact porous matrix and this asccharin glue is contacted with the polyvalent cation species of q.s, the amount of said cationic species under contact conditions, should be enough to provide at least with glue in the polyvalent cation of ionogen equivalent, the amount of this glue should be enough to form continuous film on a side of matrix, and said matrix hole should be enough little so that can form continuous film under the 15psig pressure at least.

2, the process of claim 1 wherein and flow through, cationic species is added in the fluid before walking around and contact porous matrix at fluid.

3, the method for claim 2, wherein excessive at least 0.001 mole of the Chemical Calculation equivalent of anionic group in the cation ratio glue.

4, the method for claim 3, wherein excessive at least 0.0025.

5, the method for claim 2, wherein asccharin glue is selected from the alginic acid salt, the xanthic acid salt, pectin class, carrageenan class, carboxymethyl cellulose contains the guar gum of anionic group after the modification, and the set formed of scleroglucan class.

6, the method for claim 5, wherein asccharin glue is alginates.

7, the method for claim 6, wherein multivalent metal cation is the Ca(II) or the Mg(II).

8, the method for claim 7, wherein pressure is about 15psig-50psig.

9, the method for claim 7, wherein pressure is higher than 150psig.

10, the method for claim 7 wherein adds acid for adjusting pH and reaches about 3.5-6.5.

11, the method for claim 10, wherein acid is citric acid.

12, a kind of improved film of formation on the spot on porous matrix, its aperture is little must to be enough to support a continuous film, said film contains the asccharin glue that has the negative electrical charge ionogen, its improvement is to have polyvalent cation, and this cationic equivalent should equal the molal quantity of the ionogen that exists in the glue at least.

13, the film of formation on the spot of claim 12, wherein asccharin glue is selected from alginic acid salt, xanthic acid salt, pectin class, carrageenan class, carboxymethyl cellulose, contains the guar gum of anionic group and the set that the scleroglucan class is formed after the improvement.

14, the film of formation on the spot of claim 13, wherein polyvalent cation is the Ca(II) or the Mg(II).

15, the film of formation on the spot of claim 13, wherein carrier is a porous stainless steel.

16, the film of claim 15, the wherein aperture that obtains to require through when film forms, adding fine grained.

17, the film of claim 15, wherein carrier contains from diameter 30-100 micron and aperture 0.5 to 10 micron granuloplastic porous stainless steel matrix, and the hole on the side of matrix is by the degree of depth of the sintered metal oxide powder filling of 0.2 to 1.0 micron of diameter to the 30-100 micron.