CN101049944B - Process for preparing fine zeolite particles - Google Patents
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- CN101049944B CN101049944B CN 200710096813 CN200710096813A CN101049944B CN 101049944 B CN101049944 B CN 101049944B CN 200710096813 CN200710096813 CN 200710096813 CN 200710096813 A CN200710096813 A CN 200710096813A CN 101049944 B CN101049944 B CN 101049944B
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Abstract
A process for efficiently preparing fine zeolite particles comprising synthesizing zeolite in the presence of an alkaline earth metal-containing compound and/or with controlling the preparation process of zeolite, thereby giving fine zeolite particles being composed of crystalline aluminosilicate, the fine zeolite particles having a fine average primary particle size, being excellent in the cationic exchange properties and the oil-absorbing ability, having a fine average aggregate particle size, and being excellent in the dispersibility; fine zeolite particles obtainable by the above process; and a detergent composition comprising the fine zeolite particles, the detergent composition being excellent in the detergency.
Description
The application is to be on November 9th, 2000 applying date, and application number is 00802579.7, and denomination of invention is divided an application for the application for a patent for invention of " method for preparing fine zeolite particles ".
Technical field
The present invention relates to a kind of method of fine zeolite particles, fine zeolite particles and a kind of detergent composition that comprises this fine zeolite particles that adopts this method to prepare of preparing.
Technical background
Because zeolite has ion-exchange performance, so zeolite is used as the washing buider with the form of water-softening agent always.Its ion-exchange performance depends on the initial particle size of zeolite to a great extent.Because the very thin zeolite of initial particle size has very excellent ion-exchange speed, has very high detergency ability so known zeolite.
In addition, know that fine zeolite particles has the advantage that is deposited on hardly on the clothes and can reduces turbidity, so fine zeolite particles is suitable as the washing buider.
Be disclosed method in the Japanese Patent of Sho60-127218 and Sho62-275016 when adopting at publication number, with sodium aluminate during with water glass mixing synthetic zeolite, method as this class fine zeolite particles of preparation, some have been provided under the raw material feed composition of being advised and reaction conditions (temperature and time), the example that synthesizes.When adopting the synthetic very thin zeolite of above-mentioned method, this method must be carried out under some limited raw material feed composition and reaction conditions, so low and so on the problem of productive rate occurred.
Have been reported, according at publication number being disclosed method in the Japanese Patent of Sho60-118625, add the hydro carbons of solubility, for example sucrose can make the granularity of zeolite very thin.Yet, when the inventor uses this method synthetic zeolite, even add above-mentioned soluble hydrocarbons, can not obtain to reduce the effect of initial particle size.
On the other hand, alkaline-earth metal is a kind of element that is easy in zeolite with the Na replacement.Therefore, but from a kind of viewpoint of cation sites of ion-exchange, have and manyly think that alkaline-earth metal and basic metal have the situation of equal value.Publication number is the Japanese Patent Publication of Sho55-116617, utilizes zeolite as the sorbent material with thermostability, and wherein, the sodium in the zeolite partly replaces with alkaline-earth metal.
Yet, also be described in without any report and add intentionally and forcibly alkaline-earth metal in the zeolite synthesis process, to have obtained the product of good water-softening agent effect, also to describe without any report, alkaline earth element is the requisite important element that the zeolite initial particle size is diminished.
In addition, from preparation method's angle, attempt granularity is diminished always.For example, publication number is the Japanese Patent Publication of Sho62-46494, utilizes various mixing equipment, adopts mechanical means to pulverize zeolite.Yet, from the performance of fine zeolite particles and the viewpoint of production efficiency, also have very large room for improvement.
The purpose of this invention is to provide a kind of method that effectively prepares fine zeolite particles, comprising in the presence of the alkaline including earth metal compound, and/or the method synthetic zeolite of employing control zeolite preparing process, thereby obtain the fine zeolite particles that is comprised of crystalline aluminosilicate, the mean particle size of ability, grain group that the average initial particle size of this fine zeolite particles is thin, have good cation exchange property and extremely strong absorption oil is thin, have good dispersing property; The fine zeolite particles that adopts the aforesaid method preparation is provided; With a kind of detergent composition that comprises fine zeolite particles is provided, this detergent composition has good detergency ability.
In the following description, above-mentioned purpose of the present invention and other purpose are apparent.
Summary of the invention
Particularly, the present invention relates to:
[1] a kind of method for preparing fine zeolite particles, it comprises, in the presence of the compound of alkaline including earth metal, makes the reaction of silica source and aluminium source;
[2] a kind of method for preparing fine zeolite particles, it comprises, will react in aluminium source and/or silica source adds with reactive tank is connected the circulation line;
[3] according to the method for above-mentioned [1], wherein will react in aluminium source and/or silica source adds with reactive tank is connected the circulation line;
[4] according to each the fine zeolite particles of method preparation of above-mentioned [1]-[3];
[5] a kind of detergent composition is comprising the fine zeolite particles of above-mentioned [4] item.
The accompanying drawing summary
Fig. 1 illustrates the synoptic diagram of an embodiment of fine zeolite particles equipment produced according to the present invention;
Fig. 2 illustrates the synoptic diagram of another embodiment of fine zeolite particles equipment produced according to the present invention;
Fig. 3 illustrates the synoptic diagram of another embodiment of fine zeolite particles equipment produced according to the present invention;
Fig. 4 illustrates the synoptic diagram of another embodiment of fine zeolite particles equipment produced according to the present invention;
Realize best mode of the present invention
Prepare in the method for fine zeolite particles in the present invention, mainly contain two embodiments.Particularly, first embodiment is characterised in that, in the presence of the compound of alkaline including earth metal, makes the reaction of silica source and aluminium source.On the other hand, second embodiment be characterised in that, will react in aluminium source and/or silica source adds with reactive tank is connected the circulation line.In the process of preparation fine zeolite particles of the present invention, can reduce the restriction to raw material feed composition, reaction conditions etc., thereby can according to this method, effectively prepare needed fine zeolite particles of the present invention.
In this manual, term " cation exchange property " means cationic exchange speed described in detail below and cation exchange capacity.Term " moisture liquid " means that the liquid that comprises given composition in water medium, this liquid can be got any form such as the aqueous solution, suspension and dispersion equate.Term " pipeline mixing " means in the pipeline of described feeding line and so on below, Multiple components (raw material etc.) is mixed basically.Will be described hereinafter first and second embodiments.
First embodiment at first is described.Spendable silica source and aluminium source are not subjected to concrete restriction.From the homogeneity of reaction and the viewpoint of dispersing property, preferably use silica source and aluminium source with liquid, aqueous form.Silica source comprises, the water glass that for example can buy in market.As required, can add entry or alkali metal hydroxide in water glass, the silica source of molar ratio and concentration was regulated in preparation.
In addition, the aluminium source is not subjected to concrete restriction yet.The aluminium source comprises aluminium hydroxide, Tai-Ace S 150, aluminum chloride, alkali metal aluminate such as potassium aluminate and sodium aluminate etc.Viewpoint from the hyperergy energy wherein, particularly preferably adopts sodium aluminate.Adopt these compounds as the aluminium source, where necessary, adopt alkali metal hydroxide and water, it is adjusted to suitable molar ratio and concentration.For example, can prepare the aluminium source by mixing aluminium hydroxide and sodium hydroxide in water, then heating and dissolving mixt are made sodium aluminate solution, under agitation prepared solution are added to the water, and make moisture liquid.In addition, also can in reactive tank, add water in advance, then to the alkali metal aluminate aqueous solution and the alkali metal hydroxide that wherein add high density, be adjusted to above-mentioned molar ratio and concentration.
In the compound of simultaneous alkaline including earth metal, alkaline-earth metal comprises Mg, Ca, Sr and Ba etc. in reactive system, from being convenient to buy the viewpoint of raw material and cost, adopts wherein Mg and Ca to suit.These compounds can use individually or use with the form of two kinds or multiple mixture.These compounds can join in the reactive system with the form of alkaline earth metal hydroxides or with forms such as alkaline earth metal carbonate, vitriol, muriate and nitrate.In addition, from viewpoints such as reaction homogeneities, preferably add the compound of alkaline including earth metal with liquid, aqueous form.Particularly preferably the form with water-soluble salt adopts these compounds, particularly adopts Ca, and the muriatic aqueous solution such as Mg is favourable.In the process of silica source and the reaction of aluminium source, alkaline earth metal hydroxides or alkaline earth salt should coexist at least.Particularly preferably in advance the compound of alkaline including earth metal is joined in silica source and/or the aluminium source with liquid, aqueous state.From making the very thin viewpoint of average initial particle size, even more preferably in advance the compound of alkaline including earth metal is added in the silica source.In this case, preferably add in advance the compound of all alkaline including earth metals, but also can only add a part wherein.Then, also preferably these silica source and aluminium source are mixed, carry out the zeolite synthesis reaction.
With behind zeolite synthesis, the method that replaces sodium ion with alkaline-earth metal ions is compared, in first embodiment of the present invention, in building-up process, alkaline-earth metal is added in the structure of zeolite, alkaline-earth metal is worked at the network of zeolite, thereby make the very thin zeolite of average initial particle size.According to these viewpoints, preferably make in advance alkaline-earth metal and the silica source coexistence that it is had high-affinity.In addition, wish that alkaline-earth metal participates in reaction in the starting stage of reaction and/or in crystallisation process.After crystallization finishes, add in the situation of alkaline-earth metal, can not obtain the same good fine zeolite particles that obtains with first embodiment of the present invention.
When needs are regulated the molar ratio in silica source and/or aluminium source or concentration, can adopt the compound alkali metal hydroxide described above of alkali metal containing.Except above-mentioned, these compounds can use separately.When independent use, these compounds can use in the mode identical with alkali metal-containing compound.Preferred as alkali is Na and/or K.
In this embodiment, term " in advance adding " means a kind of method, for example, before silica source and the reaction of aluminium source, the compound of alkaline including earth metal is mixed basically with silica source and/or aluminium source.
When in silica source and/or aluminium source, comprising basic metal and/or alkaline-earth metal, preferably with liquid, aqueous form, the compound of alkali metal containing and/or the compound of alkaline including earth metal are joined in silica source and/or the aluminium source, or opposite.
In first embodiment of the present invention, feed composition is such, from the viewpoint of crystal structural stability, SiO
2/ Al
20
3Molar ratio preferred 〉=0.5, more preferably 〉=1.5, and from the viewpoint of cation exchange property, SiO
2/ Al
20
3Molar ratio preferred≤6, more preferably≤4, particularly preferably≤2.5.
In addition, for the feed composition of alkaline including earth metal compound, alkaline-earth metal (Me) represents that with the form of oxide compound feed composition is such, MeO/Al
20
3The preferred 0.005-0.1 of molar ratio, to making the viewpoint of the very thin effect of average initial particle size, wherein MeO/Al
20
3Molar ratio preferred 〉=0.005, more preferably 〉=0.01, and from the viewpoint of cation exchange property, wherein, MeO/Al
2O
3Molar ratio preferred≤0.1, more preferably≤0.08, more preferably≤0.05, particularly preferably≤0.03.
For the feed composition of alkali metal-containing compound, basic metal (M) represents that with the form of oxide compound feed composition is such, M
2O/Al
20
3The preferred 0.2-8 of molar ratio, from the viewpoint of crystallization rate, wherein M
20/Al
20
3Molar ratio preferred 〉=0.2, more preferably 〉=1.5, and from the viewpoint of productive rate, wherein M
2O/Al
2O
3Molar ratio preferred≤8, more preferably≤4.In addition, as the feed composition of alkali metal-containing compound in the reactive system and water, from improving crystallization rate and making the very thin viewpoint of average initial particle size, M
2O/H
2The molar ratio of O is preferred 〉=and 0.03, more preferably 〉=0.04.In addition, from the viewpoint of cation exchange property, M
2O/H
20 molar ratio is preferred≤and 0.07, more preferably≤0.06.
From the viewpoint of productivity, in reaction process, the concentration of solids content is preferred 〉=10% (weight), more preferably 〉=15% (weight).And from the viewpoint of slurry fluidity, the concentration of solids content is preferred≤50% (weight), more preferably≤40% (weight).This paper is defined as concentration according to the solids content of the total of aqueous slurry with the concentration of solids content in the reaction process, wherein, calculate the concentration of solids content, the weight that is Si, M, Al and Me element in the supposition raw material is calculated by its oxide compound, and the raw material of adding has top given molar ratio.
The method of reacting preferred basis comprises the liquid, aqueous independent container (basic metal is included in silica source and/or aluminium source) of putting into respectively with silica source, aluminium source and alkaline including earth metal compound; The liquid, aqueous of alkaline including earth metal compound joined in silica source and/or the aluminium source; Then silica source is mixed with the aluminium source.A kind of method wherein comprises the liquid, aqueous of alkaline including earth metal compound is joined in the silica source; Then, particularly preferably resulting mixture is added in the aluminium source, or the aluminium source is added in the resulting mixture, to react.In addition, with these silica source and the mixing of aluminium source the time, from making the very thin viewpoint of mean particle size of grain group, add preferred 1-50 minute they required times, more preferably 1-20 minute.
The preferred 25-100 of temperature of reaction ℃, more preferably 40-60 ℃, particularly preferably 50-55 ℃.From the viewpoint of speed of reaction, temperature of reaction is preferred 〉=25 ℃, more preferably 〉=40 ℃, and particularly preferably 〉=50 ℃.In addition, from the energy charge of reactive tank and withstand voltage viewpoint, temperature of reaction is preferred≤100 ℃, more preferably≤60 ℃, and particularly preferably≤55 ℃.
In addition, in the reaction starting stage, by rapid gel formation reaction, make the slurries of the generation thickness that becomes.Therefore, in order to accelerate the reaction of slurries, preferably stir consumingly slurries.
Reaction times is not subjected to concrete restriction.From the viewpoint of productivity and reaction stability, count from adding all charging compositions, preferred 1-180 of reaction times minute, more preferably 2-60 minute, more preferably 4-20 minute.
After the reaction, aged mixture under agitation is to carry out crystallization.Aging temperature is not subjected to concrete restriction.From the viewpoint of crystallization rate, aging temperature is preferred 〉=50 ℃, more preferably 〉=60 ℃, and particularly preferably 〉=80 ℃.In addition, from the reactive tank energy charge and and withstand voltage viewpoint, aging temperature is preferred≤100 ℃.Digestion time is not subjected to concrete restriction.From the viewpoint of productivity, digestion time preferred 1-300 minute usually.In weathering process, preferred aging proceed to x-ray diffraction pattern climax intensity and reach till the maximum, or proceed to cation exchange capacity and reach till the maximum.
After aging the end, finish crystallization, filter and the washing slurries, or adopt in the acid and slurries.Filtering and during the washing slurries, the pH that can preferably proceed to filtrate preferably reaches≤12 till.In addition, with in the acid and during slurries, used acid is not subjected to concrete restriction.Available acid comprises sulfuric acid, hydrochloric acid, nitric acid, carbonic acid gas, oxalic acid, citric acid, tartrate, fumaric acid and succsinic acid etc.The viewpoint of the corrosion-resistant and cost of slave unit, wherein sulfuric acid and carbonic anhydride are preferred.Preferably with the pH regulator of slurries to 7-12.After crystallization finishes, make as required slurry dried, obtain fine zeolite particles of the present invention.
Secondly will illustrate that the present invention prepares second embodiment of fine zeolite particles method.The silica source of using is identical with first above-mentioned embodiment with the aluminium source.In addition, also preferred in the presence of the alkaline including earth metal compound in this embodiment, carry out the building-up reactions of zeolite.In this case, preferred in advance with the compound of alkaline including earth metal, preferably join in silica source and/or the aluminium source with moisture liquid state, more preferably in advance the compound of alkaline including earth metal is joined in the silica source.Preferred in advance the compound of all alkaline including earth metals is joined in silica source and/or the aluminium source, but also can be only the compound of a part of alkaline including earth metal be joined wherein.The example of the alkaline-earth metal that contains native alkali-metal compound and wherein comprise, and all first embodiment with above-mentioned is identical to adopt the embodiment of this compounds.
In this embodiment, term " in advance add " meant before adding silica source and aluminium source, an embodiment of a kind of method that in advance compound of alkaline including earth metal and silica source and/or aluminium source is mixed basically.An one embodiment comprises, for example, the compound of alkaline including earth metal directly joined in silica source and/or the aluminium source, and mix an embodiment of a kind of method of then silica source and aluminium source being mixed to react with it.This term also relates to another embodiment of a kind of method, wherein not needing compound with alkaline including earth metal directly to join in silica source and/or the aluminium source and with it mixes, but make the compound of alkaline including earth metal, in a part of pipeline that adds silica source and/or aluminium source, mix.An one embodiment comprises, for example, an embodiment that comprises a kind of method of carrying out the pipeline mixing, the feeding line of wherein silica source being connected with the aluminium source is being connected with the position of feeding line before the circulation line that mixes as pipeline of alkaline including earth metal compound.Adopt another kind of scheme, a kind of method can comprise that the compound with alkaline including earth metal is applied directly in the reactive tank.The compound of alkaline including earth metal participates in reaction in the reaction starting stage and/or in crystallisation process wishes.
In second embodiment of the present invention, the feed composition of each composition and above-mentioned first embodiment are basic identical.
Yet in this embodiment, in the reaction process in silica source and aluminium source, the compound that need not comprise alkaline-earth metal exists.Therefore, in this embodiment, as the feed composition of alkaline including earth metal compound, alkaline-earth metal (Me) represents that with the form of oxide compound feed composition is such, MeO/Al
20
3The preferred 0-0.1 of molar ratio, from making the viewpoint of the very thin impact of average initial particle size, wherein MeO/Al
20
3Molar ratio more preferably 〉=0.005, particularly preferably 〉=0.01, and from the viewpoint of cation exchange property, wherein MeO/Al
20
3Molar ratio more preferably≤0.08, more preferably≤0.05, particularly preferably≤0.03.
Some embodiments that comprise basic metal and/or alkaline-earth metal in silica source and/or aluminium source are identical with first above-mentioned embodiment.In addition, in reaction the concentration of solids content also first embodiment with above-mentioned is identical.
Prepare in second embodiment of fine zeolite particles method in the present invention, make the raw material that mainly comprises silica source and aluminium source, in the outer circulation pipeline that is connected with reactive tank, mix, to react.In this case, can also adopt and other raw material, the preferred compound of above-mentioned alkaline including earth metal that adopts carries out above-mentioned reaction, other raw material also with basically uniformly the form of mixture add, this mixture is mixed with other raw material and silica source and aluminium source; Or other raw material adds simultaneously with silica source and/or aluminium source; Or silica source mixed with the aluminium source, between them, begin to add respectively after the reaction.In addition, also can adopt above-mentioned and compound alkali metal containing to carry out above-mentioned reaction, the compound of alkali metal containing also can add in alkaline including earth metal compound identical mode as required.Preferably with wet mixing device (pulverizer for example; Decollator; And pulverizer, for example homogeneous state pipeline mill; The pipeline homo-mixer; High speed agitator; Static mixer; Toothed gear pump; Turbo-pump; And impeller pump) is configured to the part of circulation line pipeline, makes will each raw material to add the slurries that form behind the circulation line and can pass through circulation line.
Can be on identical or different position, circulation line is sent into from corresponding raw material tank separately in silica source and aluminium source; Adopt another kind of scheme, one of silica source and aluminium source directly can be added in the reactive tank, and in circulation line, circulate, and another kind of raw material is added circulation line from corresponding raw material tank.Any in silica source or the aluminium source can be at first added, also silica source and aluminium source can be added simultaneously.Each raw material tank is connected to the certain position of circulation line by feeding line, preferably be connected on the certain position of the circulation line that connects between reactive tank outlet and the mixer entrance, will add circulation line by feeding line from each raw material that each raw material tank adds.Adopt another kind of scheme, when one of raw material was directly added reactive tank, this raw material mixed with the another kind of raw material that adds circulation line in circulation line, circulates in circulation line from the raw material in the reactive tank.Preferably raw material is joined on the certain position of the circulation line that connects between reactive tank outlet and the mixer entrance, and mixing raw material is effectively to synthesize root tool fine zeolite particles of the present invention.In this case, preferably in reactive tank and in each raw material tank, all dispose the mixing tank that stirring rake is housed, so that slurries are more even in reactive tank, and the reinforced of raw material in the raw material tank successfully carried out.
Prepare in second embodiment of fine zeolite particles method in the present invention, comprise particularly following preparation method:
The first preparation method
This method comprises water is added in the reactive tank; With the feeding line by separately, aluminium source and silica source are added the circulation line from separately raw material tank, circulate in circulation line with water.
Preferably the compound with alkali metal containing joins in silica source and/or the aluminium source in advance; With the compound of alkali metal containing with adding simultaneously in the circulation line from silica source and/or aluminium source in the raw material tank separately; Or the compound of alkali metal containing directly added in the reactive tank.Preferably with the alkaline including earth metal compound part or all, join in the silica source in advance.The compound of alkaline including earth metal can be added in the aluminium source in advance.Adopt another kind of scheme, can add simultaneously silica source and/or the aluminium source of compound in each raw material tank of alkaline including earth metal in the circulation line; Or with the compound of alkaline including earth metal after adding in advance silica source and/or aluminium source, mix the adding circulation line by pipeline, wherein the feeding line in silica source and/or aluminium source just is connected with the feeding line of alkaline including earth metal compound on the position before the circulation line that mixes as pipeline.In addition, the compound of alkaline including earth metal directly can be added in the reactive tank.
The second preparation method
This preparation method comprises the aluminium source is added in the reactive tank; By each raw material tank feeding line separately, simultaneously silica source and water are added in the circulation line, circulate in circulation line with the aluminium source.
Preferably with the compound of alkali metal containing, add in advance in silica source and/or the water; With the compound of alkali metal containing with from silica source and the water of raw material tank add circulation line simultaneously separately; Or the compound of alkali metal containing added in the aluminium source in advance, directly add in the reactive tank again, or the compound of alkali metal containing is added in the reactive tank simultaneously with the aluminium source.Preferably the compound with part or all alkaline including earth metal adds in the silica source in advance.Adopt another kind of scheme, can with the compound of alkaline including earth metal with silica source, from raw material tank separately, add circulation line simultaneously; Or at the compound with alkaline including earth metal, after joining in advance in the silica source by the pipeline mixing, the compound of alkaline including earth metal is added circulation line, wherein the feeding line of silica source just on the position before the circulation line that mixes as pipeline, is connected with the feeding line of alkaline including earth metal compound.In addition, the compound of alkaline including earth metal can be added in advance in the aluminium source, directly add again in the reactive tank, maybe the compound of alkaline including earth metal can be added in the reactive tank simultaneously with the aluminium source.In addition, the compound of alkaline including earth metal can be added with water.
The third preparation method
This method comprises silica source is added in the reactive tank; By each raw material tank feeding line separately, aluminium source and water are added circulation line simultaneously, circulate in circulation line with silica source.
Preferred in advance with the compound of alkali metal containing, add in aluminium source and/or the water; With the compound of alkali metal containing, with from separately aluminium source and/or the water of raw material tank, add simultaneously circulation line; Or the compound of alkali metal containing added in the silica source in advance, directly add in the reactive tank again, or with the compound of alkali metal containing with silica source, add in the reactive tank simultaneously.Preferably with the alkaline including earth metal compound part or all, add in the silica source in advance.The compound of alkaline including earth metal can be added in the silica source in advance, directly adds in the reactive tank again, or with the compound of alkaline including earth metal with silica source, add in the reactive tank simultaneously.Adopt another kind of scheme, the compound of alkaline including earth metal can be added after the aluminium source in advance, add circulation line, or with the compound of alkaline including earth metal, add circulation line from corresponding raw material tank separately simultaneously with the aluminium source; Maybe the compound of alkaline including earth metal can be added in advance after the aluminium source, mix by pipeline again and add circulation line, wherein the feeding line in aluminium source just on the position before being used as the circulation line of mixing line, is connected with the feeding line of alkaline including earth metal compound.In addition, the compound of alkaline including earth metal can be added with water.
Particularly when principal reaction is carried out in reactive tank, above-mentioned first to the third preparation method be preferred embodiment.
Can be according to circular flow and the feed rate of every kind of raw material, the blending ratio in silica source and aluminium source in the adjusting circulation line, blending ratio is with SiO
2/ Al
2O
3Molar ratio represents, from the viewpoint of the ability that absorbs oil, blending ratio is preferred 〉=and 0.1, more preferably 〉=0.5, particularly preferably 〉=1.And from the viewpoint of slurry performance, blending ratio is preferred≤3, more preferably≤2.5, particularly preferably≤2.
With the same in the second and the third preparation method, silica source or aluminium source are being added in the reactive tank, and with other raw material adding circulation line, in circulation line, circulate when reacting with silica source or aluminium source, because the increase of product proportion may have blending ratio with situation about changing by the time in the reaction process.In this case, the concentration of adjusting raw material and circular flow etc. make when beginning to add other material, with SiO
2/ Al
2O
3The raw material blending ratio that molar ratio represents is preferably 0.1-3, more preferably 0.5-2.5, and particularly preferably 1-2 according to this method of the present invention, can prepare needed fine zeolite particles.The blending ratio here (molar ratio), calculated by following formula:
Blending ratio=(Qs * Cs)/(Qa * Ca)
Qa is the flow (kg/min) in aluminium source in the formula; Ca is contained Al in the aluminium source
2O
3Volumetric molar concentration (mol/kg); Qs is the flow (kg/min) of silica source; With Cs be contained SiO in the silica source
2Volumetric molar concentration (mo l/kg).
Here temperature of reaction, violent stirring, the reaction times of reaction initial stage and make the method for crystallization of zeolites, first embodiment with above-mentioned is identical basically.Yet in this embodiment, the crystallization of zeolite is actually after reaction finishes, and in circulation line circulation or not in the situation of loop slurry is undertaken by aging.Behind aging the end, stop crystallization, adopts the method identical with first embodiment, slurries are also washed in filtration, or with in the acid and slurries, to obtain fine zeolite particles of the present invention.
The method for preparing fine zeolite particles of the present invention, particularly preferred embodiment is first embodiment and above-mentioned second embodiment that embodiment combines.In other words, this preferred embodiment comprises, in the circulation line that the aluminium source is connected with silica source with reactive tank is connected, in the presence of the compound of alkaline including earth metal, makes the reaction of aluminium source and silica source.The compound of above-mentioned alkaline including earth metal is existed in reactive system, for example, in advance the compound of alkaline including earth metal is added in aluminium source and/or the silica source, more preferably in advance the compound of alkaline including earth metal be added in the silica source.Above-mentioned alkaline-earth metal, preferred Ca and/or Mg.As for the feed composition of alkaline including earth metal compound, alkaline-earth metal (Me) represents that with the form of oxide compound its feed composition is such, MeO/Al
20
3The preferred 0.005-0.1 of molar ratio, to making the viewpoint of the very thin effect of average initial particle size, wherein MeO/Al
20
3Molar ratio preferred 〉=0.005, more preferably 〉=0.01, and from the viewpoint of cation exchange property, MeO/Al
2O
3Molar ratio preferred≤0.1, more preferably≤0.08, more preferably≤0.05, particularly preferably≤0.03.In addition, can use in the same manner as described above the compound of alkali metal containing.Its feed composition can be with above-mentioned identical.In this embodiment, term " in advance add ", its implication is identical with implication in second embodiment for preparing fine zeolite particles method of the present invention.
According to this embodiment, make the reaction of aluminium source and silica source, even when the concentration of solids content is high especially in reaction process, also can effectively prepare needed fine zeolite particles of the present invention.In addition, from improving the viewpoint of the oily ability of cation exchange property and absorption, this embodiment is particularly preferred.When concentration 〉=25% (weight) of solids content in the reaction process, in addition in concentration up to 〉=30% the time, this embodiment is effective especially, can effectively prepare needed fine zeolite particles of the present invention.
Adopt the method for above-mentioned preparation fine zeolite particles of the present invention, prepared fine zeolite particles of the present invention, its anhydrous form preferably has following general formula:
xM
2O·ySiO
2·Al
20
3·zMeO，
M is basic metal in the formula; Me is alkaline-earth metal; X is numeral, is 0.2-2; Y is numeral, is 0.5-6; With z be the numeral, be 0.005-0.1.
From being convenient to buy the viewpoint of raw material and cost, in the superincumbent composition, M is Na and/or K more preferably, particularly preferably Na.The preferred Ca of Me and/or Mg.In addition, from making the very thin viewpoint of average initial particle size, digital x is 0.6-1.3 more preferably, and digital y is 0.9-5 more preferably, and z preferably 〉=0.005.From cation exchange property, namely from the viewpoint of cationic exchange speed and cation exchange capacity, z is preferred≤0.1, more preferably≤0.08, and 0.01-0.03 particularly preferably.In second embodiment, in the process of silica source and alumina source reaction, needn't there be alkaline-earth metal to exist.Therefore, the z value in the above-mentioned general formula, preferred 0-0.1, the z value of stipulating in above-mentioned scope is preferred.
In addition, adopt the fine zeolite particles of the present invention of method preparation of the present invention, have known crystalline form, such as A-type, X-type, Y-type and P-type zeolite etc. are arranged.Crystalline form is not subjected to concrete restriction.From the viewpoint of cation exchange property, preferred X-type and A-type zeolite, more preferably A-type zeolite.The crystalline phase that these zeolites generate can be single-phase or mixed phase.
The average initial particle size of fine zeolite particles of the present invention is that the mean value of fixed side's diameter of forming with the tangent (Feret diameter) that obtains according to scanning electronic microscope (SEM) is determined.From the viewpoint of cationic exchange speed, average initial particle size is preferred≤1.5 μ m, more preferably≤1.3 μ m.In addition, average initial particle size is preferred 〉=0.2 μ m, more preferably 〉=0.5 μ m, because when average initial particle size was too small, degree of crystallinity descended, the mean particle size of grain group increases.
The term of fine zeolite particles of the present invention " cationic exchange speed " means the Ca loading capacity that the particulate zeolite per minute has.From the viewpoint of detergency ability, cationic exchange speed is preferred 〉=150mg CaCO
3/ g, more preferably 〉=170mg CaCO
3/ g.On the other hand, term " cation exchange capacity " means the Ca loading capacity that particulate zeolite of the present invention had in per 10 minutes.From the viewpoint of detergency ability, cation exchange capacity is preferred 〉=150mg CaCO
3/ g, more preferably 〉=180mg CaCO
3/ g, particularly preferably 〉=200mg CaCO
3/ g.
The mean particle size that fine zeolite particles grain of the present invention is rolled into a ball is by mensuration such as laser diffraction-sweep type particle size distribution analysis instrument.From preparation during washing composition, the dispersing property of fine zeolite particles and on clothes the viewpoint of deposition properties, the mean particle size of grain group is preferred≤13 μ m, more preferably≤7 μ m, particularly preferably 1-5 μ m.
In the present invention, also scattering parameter is defined as average initial particle size (μ m) and rolls into a ball the product of mean particle size (μ m) with grain.The scattering parameter of these zeolites is preferred≤and 7, more preferably 0.1-5, cationic exchange speed is general 〉=150mg CaCO
3/ g is so they are suitable as particulate zeolite of the present invention.
In addition, represent with X μ m in average initial particle size, when grain group mean particle size represented with Y μ m, wherein X and Y satisfied 0.6≤X≤1.5, preferably satisfied 0.7≤X≤1.2, more preferably satisfy 0.8≤X≤1.0 relations, and satisfy 20X/3-2.4≤Y≤15 relations, wherein digital Y preferably satisfies≤12, more preferably satisfies≤10, and because they generally all have the ability of extremely strong absorption oil, be preferred so satisfy X≤Y relation.In prepared fine zeolite particles, when X and Y satisfied above-mentioned the relation, often average initial particle size was very thin, and a grain group mean particle size obtains suitable improvement.Therefore can cause simultaneously " formation in gap between particle " and " exposure on primary particles surface ", thereby the ability of imagination absorption oil improves.
As describing in detail at embodiment, the ability that absorbs oil represents with the amount that absorbs oleum lini.The ability that absorbs oil is preferred 〉=50ml/100g, more preferably 〉=70ml/100g, particularly preferably 80-130ml/100g.From the viewpoint of dispersing property again, for the absorption oil ability of above-mentioned scope, fine zeolite particles is preferred.
Fine zeolite particles of the present invention has very thin average initial particle size, excellent cation exchange property and excellent absorption oil ability, very thin grain rolled into a ball mean particle size and excellent dispersing property.Therefore, this fine zeolite particles is suitable as the soil improvement agent of filler, resin extender, water conditioner, washing buider, oxygen-nitrogen separating agent, gardening of papermaking and rumbling compound etc., and this fine zeolite particles is especially suitable for use as the washing buider.
Secondly, adopt fine zeolite particles of the present invention as the detergent composition of washing buider explanation.In detergent composition, the content of fine zeolite particles is not subjected to concrete restriction.From having the viewpoint of enough detergency abilities, its content is preferred 〉=1% (weight), more preferably 〉=3% (weight), particularly preferably 〉=10% (weight).In addition, from preventing that washings is muddy and deposit to viewpoint on the clothes, its content is preferred≤80% (weight), more preferably≤70% (weight), particularly preferably≤60% (weight).
Above-mentioned detergent composition also can comprise tensio-active agent.Tensio-active agent is not subjected to concrete restriction.Tensio-active agent comprises, such as nonionic surface active agent, aniorfic surfactant, cationic surfactant and amphoteric surfactant etc.
The specific examples of nonionic surface active agent comprises, for example, Tokkyocho Koho in the Japan Office publication: the known nonionic surface active agent described in " Shuchi Kanyo Gijutsu (powder detergent that is used for clothes), 3-1 chapter ".
Polyethylene oxide and/or poly(propylene oxide) type nonionogenic tenside are particularly preferred, with the oxyethane of average 5-15 mole, are added to the Voranol EP 2001 for preparing in primary alconol with 8-16 carbon atom or the secondary alcohol, are particularly preferred.
Other nonionic surface active agent comprises polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, sucrose fatty ester, fatty mono glyceride, higher Marlamid, the higher Marlamid of polyoxyethylene, amine oxide, alkylglycoside, alkyl glycerol base ether and N-alkyl glucose amide etc.
Anion surfactant comprises, the TokkyochoKoho that for example publishes at Japan Office: the known tensio-active agent described in " Shuchi Kanyo Gijutsu (powder detergent that is used for clothes), 3-1 chapter ".
Concrete, be selected from alkylbenzene sulfonate, alkyl sulfuric ester salt and thiazolinyl sulfuric acid, the Voranol EP 2001 sulfuric acid (average mol of ethylene oxide: 0.5-6), one or more aniorfic surfactant of alkyl Monophosphate salt and soap are preferred, wherein each all has straight or branched, alkyl or alkenyl on average has 8-22 carbon atom, and alkylbenzene sulfonate wherein and alkylsulfonate are particularly preferred.
The gegenion of these anion surfactants is selected from sodium ion, potassium ion, magnesium ion, calcium ion, amine such as thanomin, quaternary ammonium salt, and the positively charged ion of their mixture proton generation.When adopting above-mentioned aniorfic surfactant, can adopt a kind of like this method, for example comprising the form that aniorfic surfactant is mixed with acid, and separately alkali is added wherein.
Positively charged ion shape tensio-active agent comprises, the TokkyochoKoho that for example publishes at Japan Office: the known cationic surfactant described in " Shuchi Kanyo Gijutsu (powder detergent that is used for clothes), 3-1 chapter ".Preferably cationic surfactant comprises, for example quaternary ammonium salt, for example quaternary ammonium salt of benzalkonium type.
Amphoteric surfactant comprises, the TokkyochoKoho that for example publishes at Japan Office: some the known amphoteric surfactant described in " Shuchi Kanyo Gijutsu (powder detergent that is used for clothes), 3-1 chapter ".Preferred amphoteric surfactant comprises, such as the amphoterics of alkyl betaine-type etc.
Above-mentioned tensio-active agent can use separately, or uses with the form of two kinds or multiple mixture.In addition, be selected from the kinds of surface promoting agent in the situation of aniorfic surfactant, these tensio-active agents can be selected from the tensio-active agent of same type, or be selected from the kinds of surface promoting agent in the situation of aniorfic surfactant and nonionic surface active agent, these tensio-active agents can be selected from various dissimilar tensio-active agents.
In detergent composition of the present invention, the content of tensio-active agent is not subjected to concrete restriction.From the viewpoint of detergency ability, the content of tensio-active agent is preferred 〉=1% (weight), more preferably 〉=5% (weight), particularly preferably 〉=10% (weight).In addition, from the viewpoint of flushing performance, the content of tensio-active agent is preferred≤80% (weight), more preferably≤60% (weight), particularly preferably≤50% (weight).
In addition, can in comprising the detergent composition of fine zeolite particles of the present invention, suitably allocate the various additives of usually in cloth-washing detergent, allocating into into.Its content suitably can be adjusted in the scope of not damaging the required effect of detergent composition of the present invention.
Above-mentioned additive can be the general additive that adopts of washing composition, without any restriction.These additives comprise, for example inorganic chelator as the zeolite (average initial particle size surpasses the zeolite of 1.5 μ m) that on market, can buy, unbodied aluminosilicate, crystalline silicate, unbodied silicate, tripoly phosphate sodium STPP and and Starso; The poly-acetate of organic sequestering agent such as amino and polyacrylate; Anti-sludging agent such as carboxymethyl cellulose; Water-soluble organic solvent such as polyoxyethylene glycol and glycerine; Basifier such as yellow soda ash and salt of wormwood; Enzyme such as proteolytic enzyme, lipase, cellulase and amylase; SYNTHETIC OPTICAL WHITNER such as SPC-D and Sodium peroxoborate; Bleach activator; Sodium salt such as sodium sulfate and sodium-chlor; Antioxidant; Clay mineral; Fluorescigenic dyestuff; Bluing agent; With spices etc.
According to a kind of known method, can prepare detergent composition of the present invention, comprising, as required, adopt stirring means to mix each above-mentioned composition, and granulation etc.Because prepared detergent composition comprises fine zeolite particles of the present invention, so said composition has very excellent detergency ability.Can estimate detergency ability according to following EXPERIMENTAL EXAMPLE.
Adopt the measured value in following method mensuration embodiment and the Comparative Examples." % " of this paper means " % by weight ".In each table, the unit of cationic exchange speed and cation exchange capacity all uses " mg/g " expression simply.In addition, except as otherwise noted, in embodiment and Comparative Examples, all use sodium aluminate with the form of sodium aluminate aqueous solution.
(1) cationic exchange speed
Calculate with anhydride, take by weighing exactly the 0.04g sample, it is added in 100ml calcium chloride water in the 100ml beaker (with CaCO
3Calculate, calcium concn is 100ppm) in, then 20 ℃ of lower stirrings 1 minute.Then, adopting hole dimension is the film filter filtering mixt of 0.2 μ m.Get 10ml filtrate, adopt the Ca content in the EDTA titration method analysis filtrate, measure the Ca amount of 1g sample ion-exchange in 1 minute (with CaCO
3Calculate), as speed (the mg CaCO of cationic exchange
3/ g).
(2) cation exchange capacity
Calculate with anhydride, take by weighing exactly the 0.04g sample, it is added in 100ml calcium chloride water in the 100ml beaker (with CaCO
3Calculate, calcium concn is 100ppm) in, then 20 ℃ of lower stirrings 10 minutes.Then, adopting hole dimension is the film filter filtering mixt of 0.2 μ m.Get 10ml filtrate, adopt the Ca content in the EDTA titration method analysis filtrate, measure the Ca amount of 1g sample ion-exchange in 10 minutes (with CaCO
3Calculate), as capacity (the mg CaCO of cationic exchange
3/ g).
(3) average initial particle size
Adopt digitizer (on market, can buy " digitizer KW3300 " from Graphtic company), measure average initial particle size (μ m; The mean value of 〉=50 particles), and employing field emission high resolution scanning electron microscope (FE-SEM can buy from company limited of Hitachi (Hitachi) on market, S-400), and the shooting scanning electron photomicrograph.
(4) mean particle size of grain group
Adopt ultrasonication that sample is dispersed in as in the ion exchanged water of dispersion medium 1 minute, then adopt laser diffraction/scattering particle size distribution analysis instrument (on market, can buy from HORIBA company limited, LA-700), measure the size-grade distribution of particle, with the median diameter of the trying to achieve mean particle size (μ m) as grain group.
(5) absorb oily ability
Employing is obtained the ability (ml/100g) that absorbs oil according to the method for JIS K 5101 with the form that absorbs flax oil mass.
(6) crystalline form
Adopt x-ray diffractometer (on market, can buy from K.K.Rigaku model: RAD-200), under the condition of CuK α-ray, 40kV and 200mA, measure x-ray diffraction pattern.According to the X-ray crystallogram that JCPDS (about the joint committee of powdery diffractometry standard) proposes, estimate qualitatively the x-ray diffraction pattern of measuring.
With the NaOH of 1297.2g48% join 2 liters of removable stainless steel cylinders (internal diameter: 12cm), then, under agitation with 1000g aluminium hydroxide (purity: 99%) add wherein.Then heat up, under 120 ℃ with mixture heating up 1 hour.Then, with the mixture cooling, obtain sodium aluminate (Na
2O:21.01%, Al
20
3: 28.18%).
With adopting the 320g sodium aluminate of aforesaid method preparation, put into another removable stainless steel cylinder of 2 liters, then to the NaOH that wherein adds 316.1g48%.Adopt this mixture as the aluminium source.
Secondly, with No. 3 water glass (Na of 355.6g
20:9.68%, SiO
2: 29.83%) put into another removable stainless steel cylinder of 2 liters, under agitation previously prepared calcium chloride water is added wherein, calcium chloride water is in advance with the water of 818.2g ion-exchange and 1.96g Calcium Chloride Powder Anhydrous mixed preparing.Adopt the water glass solution of preparing, as the silica source of alkaline including earth metal.Here No. 3 water glass that adopt are bought from Osaka Keiso company on market.
Above-mentioned aluminium source is heated to 50 ℃, stirs under 300rpm with stirring rake, diameter of stirring paddle is 11cm.In addition, silica source is heated to 50 ℃ equally.When these two kinds of raw materials reach 50 ℃, adopt peristaltic pump in 5 minutes, silica source to be added drop-wise in the aluminium source.After dripping end, keeping temperature is 50-60 ℃, reacts 10 minutes.Then reaction mixture is heated to 80 ℃, then 80 ℃ and stir under aging 1.5 hours.In reaction process, the concentration of solids content is 23%.In addition, Na
2O/H
20 molar ratio is 0.05.
Filter made slurries, wash with water, until the pH of filtrate reaches till 11.4.Then the residue with gained descended dry 13 hours at 100 ℃, made zeolite powder.
Made zeolite consists of 1.09Na under anhydrous state
2O2.05SiO
2Al
20
3(0.02CaO x=1.09, y=2.05 and z=0.02).In addition, according to the result of x-ray diffraction pattern, the crystalline form that obtains is the A-type, and this zeolite belongs to ASTM No.38-241.
In addition, the average initial particle size of made fine zeolite particles is 0.87 μ m, and cationic exchange speed is 184mg CaCO
3/ g, cation exchange capacity are 219mg CaCO
3/ g demonstrates excellent cation exchange property.In addition, the mean particle size of fine zeolite particles grain group is 4.2 μ m, and the ability that absorbs oil is 53ml/100g.
Embodiment 2-6
Adopt the method identical with embodiment 1 synthetic and estimate zeolite, adopt the method identical with embodiment 1 to prepare aluminium source and silica source, silica source is based on the inlet amount shown in the table 1 and adds different Ca measure in water glass.So, making the A-type fine zeolite particles shown in the table 2, its average initial particle size is 0.75-1.3 μ m.
Comparative Examples 1
Adopt the method identical with embodiment 1 synthetic and estimate zeolite, different is, synthesizes to be to carry out according to the feed composition shown in the table 1, does not add alkaline-earth metal.As a result, as shown in table 2, in the situation that does not add alkaline-earth metal, average initial particle size is greatly to 1.8 μ m, and cationic exchange speed is low to moderate 130mg CaCO
3/ g.
Comparative Examples 2
The 3.5g zeolite that will synthesize in Comparative Examples 1 adds in 1 liter the Calcium Chloride Powder Anhydrous aqueous solution of 333mg/1, and the mixture that obtains was stirred 10 minutes.Then, adopting hole dimension is the film filter filtering mixt of 0.2 μ m, then with 1 residue that lifts away from the water washing gained that son exchange, descends drying 13 hours at 100 ℃.Shown in the product in the table 2 forms, although the calcium in the made zeolite by ion-exchange, does not have to find to cause owing to ion-exchange the variation of average initial particle size.
Table 1
-continued-
-continuous-
Table 2
-continued-
-continuous-
Embodiment 7
Adopt reaction and the method identical with embodiment 1, and the prepared aluminium source identical with embodiment 1 quantity and silica source synthesize and estimate zeolite, the time of adding silica source is changed into 20 minutes (table 3).So, make A-type fine zeolite particles as shown in table 4, even the mean particle size of grain group is slightly large, cationic exchange speed is also excellent.
Embodiment 8
Adopt the reaction identical with embodiment 7 and method to synthesize and estimate zeolite, the alkaline earth salt of adding is Magnesium Chloride Anhydrous (table 3).So make A-type fine zeolite particles as shown in table 4, made similar of this fine zeolite particles and embodiment 7.
Comparative Examples 3
Adopt the reaction identical with embodiment 7 and method to synthesize and estimate zeolite.Yet, in building-up process, do not add alkaline-earth metal (table 3).As a result, as shown in table 4, the mean particle size of grain group is greatly to 28.3 μ m, and cationic exchange speed is low to moderate 97mg CaCO
3/ g.
Table 3
-continued-
-continuous-
Table 4
-continued-
-continuous-
Adopt the method identical with embodiment 1 to synthesize and estimate zeolite, difference is, with feed composition Na
2O/A l
20
3(molar ratio) changes into 3 (tables 5).In reaction process, Na
2O/H
20 molar ratio is 0.04.As shown in table 6, made product is A-type zeolite, even the average initial particle size of made zeolite is 1.3 μ m, is slightly larger than the average initial particle size of embodiment 1 zeolite, but its cationic exchange speed also the zeolite with embodiment 1 is the same high.
Comparative Examples 4
Adopt the method identical with embodiment 9 to synthesize and estimate zeolite.Yet, in building-up process, do not add alkaline-earth metal (table 5).As a result, as shown in table 6, to 2.2 μ m, cationic exchange speed is low to moderate 90mg CaCO to the average initial particle size of made zeolite greatly
3/ g.
Table 5
-continued-
-continuous-
Table 6
-continued-
-continuous-
The below will according to the equipment shown in Fig. 1-4 usefulness synoptic diagram, illustrate each equipment that the preparation zeolite uses in embodiment 10-15.Use the equipment shown in each figure to synthesize fine zeolite particles, wherein these equipment comprise the reactive tank that agitator is housed and the outer circulation pipeline that disposes mixing tank at a part of path.At raw material tank, feeding line, circulation line and the reactive tank shown in each figure, can both suitably control temperature, but the device of not shown control temperature.
Equipment shown in Figure 1 comprises 80 liters stainless steel reaction groove 3, and this groove is equipped with outer circulation pipeline 6, and the outer circulation pipeline has mixing tank 5 (pipeline mill; On market, model: LM-S) can be bought from TokushuKika Kogyo company limited.Adopt infusion pump 9 (on market, can buy WP pump, model: WP2SS042C0), liquid is transported to the circulation line 6 from reactive tank 3 from Dydo metal company limited.Can pass through respectively feeding line 7 and 8, just on the position before mixing tank 5 entrances, raw material be added from raw material tank 1 and 2 (two all is 80 liters of stainless steel tanks).In addition, raw material can respectively from raw material tank 1 and 2, arbitrarily add circulation line 6.Reactive tank 3 is equipped with an agitator 4 (actual is to use) under the rotating speed of 100rpm, the diameter of stirring rake is 210mm. Raw material tank 1 and 2 also all is equipped with and top identical agitator (not shown in Fig. 1).
The structure of equipment shown in Figure 2 makes raw material respectively by feeding line 7 and 8, before raw material tank 10 and 11 adding circulation lines 6, confluxes by feeding line 7 and 8 first, raw material is carried out pipeline mix.Adopt another scheme, also can only adopt a raw material tank.Available infusion pump 9 (on market, can buy from Dydo metal company limited, the WP pump, model: WP3WL140C0), the liquid from reactive tank 12 delivery cycle pipelines 6. Raw material tank 10 and 11 all is 200 liters stainless steel tank, reactive tank 12 is stainless steel tanks of 350 liters, internal diameter is 750mm, and mixing tank 14 is that line mixer (line mixer) (can be bought model: 2S6) from TokushuKika Kogyo company limited on market.In raw material tank 10 and 11, all dispose an agitator (actual is to use) under the 100rpm rotating speed, diameter of stirring paddle is 210mm, at agitator 13 of reactive tank 12 interior configurations (actual is to use under the 100rpm rotating speed), agitator 13 includes inclination angle type blade and anchor impeller, and the diameter of each blade is 500mm.This paper is not shown raw material tank 10 and 11 agitator in Fig. 2.
Equipment shown in Figure 3 comprises 200 liters stainless steel reaction groove 16, and this reactive tank is equipped with outer circulation pipeline 19, wherein has mixing tank 18.Available infusion pump 21 (can be bought WP pump, model: WP2SS040C0), liquid is transported to the circulation line 19 from reactive tank 16 from Dydo metal company limited on market.Can pass through feeding line 20, raw material is added just in mixing tank 18 (line mixer from raw material tank 15 (200 liters of stainless steel tanks); On market, model can be bought from Tokushu Kika Kogyo company limited: the 2S6) position before the import.In addition, configuration has the agitator 17 (actual is to use) of maximum mixed type stirring rake under the rotating speed of 100rpm in reactive tank 16, and diameter of stirring paddle is 340mm.Dispose agitator (actual is to use under the rotating speed of 100rpm) in raw material tank 15, the diameter of stirring rake is 210mm (not shown in Fig. 3).
Equipment shown in Figure 4 comprises 350 liters stainless steel reaction groove 23, and this groove is equipped with outer circulation pipeline 26, wherein has mixing tank 25.Adopt infusion pump 28 (on market, can buy WP pump, model: WP3WL140C0), liquid is transported to the circulation line 26 from reactive tank 23 from Dydo metal company limited.Can pass through feeding line 27, raw material from raw material tank 22 (2001 stainless steel tank), is added to just in mixing tank 25 (line mixer; On market, model can be bought from Tokushu Kika Kogyo company limited: the 2S6) position before the import.In addition, configuration agitator 24 (actual is to use under the rotating speed of 100rpm) in reactive tank 23, agitator 24 comprises inclination angle type blade and anchor impeller, the diameter of each blade is 500mm.Dispose agitator (actual is to use under the rotating speed of 100rpm) in raw material tank 22, the diameter of stirring rake is 210mm (not shown in Fig. 4).
According to each equipment shown in Fig. 1-4, all will be transported to liquid the circulation line from reactive tank, turn back in the reactive tank again.In equipment shown in Figure 3, can see that from this figure liquid turns back to the reactive tank from the sidewall of reactive tank, liquid dispersion is entered in the liquid of reactive tank.On the other hand, in the equipment shown in Fig. 1,2 and 4, the liquid of carrying from reactive tank is to return from the top of reactive tank by circulation line, and liquid dispersion is entered in the liquid of reactive tank.
Adopt equipment shown in Figure 1.No. 3 water glass are put into raw material tank 1; Aqueous sodium hydroxide solution with 48% and sodium aluminate are put into raw material tank 2; Again 35% calcium chloride solution and the water of ion-exchange are put into reactive tank 3.Under agitation with the heating material to 50 in each groove ℃, until till stirring.Using infusion pump 9, when being transported to first the calcium chloride solution in the reactive tank 3 in the circulation line 6, and start agitator 4, simultaneously by feeding line 7 and 8, with the aluminium source (sodium aluminate solution in the silica source in the raw material tank 1 (water glass) and the raw material tank 2, comprise 48% aqueous sodium hydroxide solution and sodium aluminate), in 2.2 minutes, add simultaneously in the circulation line 6, react.In reaction process, the rotating speed of mixing tank 5 is 1800rpm.After reaction finished, made slurries stopped circulation.Then slurries are heated to 80 ℃, aging 1.5 hours in this state.Dope filtration with made washes with water, until the pH of filtrate reaches till 11.4.Then, the residue of gained is dry, obtain zeolite powder.Feed conditions and reaction conditions are shown in table 7, and composition and the character of made zeolite are shown in table 8.Na
2O/H
20 molar ratio is 0.04.
Adopt equipment shown in Figure 2.No. 3 water glass are put into raw material tank 10; Calcium chloride solution with 35% and the water of ion-exchange are put into raw material tank 11; Aqueous sodium hydroxide solution with 48% and sodium aluminate are put into reactive tank 12.Under agitation with the heating material to 50 in each groove ℃, until till stirring.Using infusion pump 9, with the aluminium source (sodium aluminate solution in the reactive tank 12, comprise 48% aqueous sodium hydroxide solution and sodium aluminate) when being transported to first in the circulation line 6, and start agitator 13, simultaneously by feeding line 7 and 8, calcium chloride solution with in the silica source in the raw material tank 10 (water glass) and the raw material tank 11 added in the circulation line 6 in 4 minutes simultaneously, reacted.In reaction process, the rotating speed of mixing tank 14 is 3600rpm.Even after reaction finishes, also continue the made slurries of circulation in circulation line 6, slurries are heated to 80 ℃ simultaneously, the maintenance slurries are lower aging 1.5 hours at 80 ℃.Filter made slurries, wash with water, until the pH of filtrate reaches till 11.4.Then the residue of gained is dry, obtain zeolite powder.Feed conditions and reaction conditions are shown in table 7, and composition and the character of made zeolite are shown in table 8.Na
2O/H
20 molar ratio is 0.06.
Embodiment 12
Adopt equipment shown in Figure 2.Aqueous sodium hydroxide solution with 48% and sodium aluminate are put into raw material tank 10; Calcium chloride solution with 35% and the water of ion-exchange are put into raw material tank 11; No. 3 water glass are put into reactive tank 12.Under agitation with the heating material to 50 in each groove ℃, until till stirring.When being transported to first the silica source in the reactive tank 12 (water glass) in the circulation line 6 with infusion pump 9, and start agitator 13, simultaneously respectively by feeding line 7 and 8, with the aluminium source (sodium aluminate solution in the raw material tank 10, comprise 48% aqueous sodium hydroxide solution and sodium aluminate) and raw material tank 11 in calcium chloride solution, in 7 minutes, add simultaneously in the circulation line 6, react.In reaction process, the rotating speed of mixing tank 14 is 3600rpm.Even after reaction finishes, also continue the made slurries of circulation in circulation line 6, slurries are heated to 80 ℃ simultaneously, the maintenance slurries are lower aging 1.5 hours at 80 ℃.Filter made slurry, wash with water, until the pH of filtrate reaches till 11.4.Then the residue of gained is dry, obtain zeolite powder.Feed conditions and reaction conditions are shown in table 7, and composition and the character of made zeolite are shown in table 8.Na
2O/H
20 molar ratio is 0.06.
Embodiment 13
Adopt the method identical with embodiment 12, synthetic zeolite in the situation of not using calcium chloride.Feed conditions and reaction conditions are shown in table 7, and composition and the character of made zeolite are shown in table 8.
Embodiment 14
Adopt equipment shown in Figure 3.No. 3 water glass are put into raw material tank 15 and stirring.Then, with the calcium chloride solution that in advance water of 35% calcium chloride solution and ion-exchange is mixed with, in 1 minute, add in the raw material tank 15, then with the mixture heating up to 50 of gained ℃.Then after starting agitator 17, and the aqueous sodium hydroxide solution of sodium aluminate and 48% put into reactive tank 16, with the mixture heating up to 50 of gained ℃.After heating, adopt infusion pump 21 circulation aluminium source (sodium aluminate solution in circulation line 19, the aqueous sodium hydroxide solution that comprises sodium aluminate and 48%), simultaneously by feeding line 20, with the silica source (water glass solution in the raw material tank 15, wherein comprise No. 3 water glass and calcium chloride solution), in 3.5 minutes, add in the circulation line 19, react.In reaction process, the rotating speed of mixing tank 18 is 3600rpm.Even after reaction finishes, also continue the made slurries of circulation in circulation line 19, slurries are heated to 80 ℃ simultaneously, slurry remains on 80 ℃ of lower wearing out 2 hours.Filter the slurries of gained, wash with water, until the pH of filtrate reaches till 11.4.Then the residue of gained is dry, obtain zeolite powder.Feed conditions and reaction conditions are shown in table 7, and composition and the character of made zeolite are shown in table 8.Na
2O/H
20 molar ratio is 0.06.
Adopt equipment shown in Figure 4.No. 3 water glass are put into raw material tank 22 and stirring, then, 48% aqueous sodium hydroxide solution is put into raw material tank 22.Then, in advance with 35% the calcium chloride solution calcium chloride solution with the water mixed preparing of ion-exchange, in 1 minute adding wherein, with the mixture heating up to 50 of gained ℃.Then start agitator 24, and sodium aluminate is put into reactive tank 23, be heated to 50 ℃.After heating, adopt infusion pump 28 circulation aluminium source (sodium aluminate) in circulation line 26, simultaneously by feeding line 27, with the silica source (water glass solution in the raw material tank 22, wherein comprise No. 3 water glass, 48% aqueous sodium hydroxide solution and calcium chloride solution), in 8 minutes, add in the circulation line 26, react.In reaction process, the rotating speed of mixing tank 25 is 2400rpm.Even after reaction finishes, also continue the made slurries of circulation in circulation line 26, slurries are heated to 80 ℃ simultaneously, slurries remain on 80 ℃ of lower wearing out 1 hour.Filter the slurries of gained, wash with water, until the pH of filtrate reaches till 11.4.Then the residue of gained is dry, obtain zeolite powder.Feed conditions and reaction conditions are shown in table 7, and composition and the character of made zeolite are shown in table 8.Na
2O/H
20 molar ratio is 0.06.
Table 7
*SiO in circulation line
2/ Al
2O
3Molar ratio
Table 8
-continued-
-continuous-
Compare with Comparative Examples 1-4, can find out from embodiment 1-15, the method of fine zeolite particles produced according to the present invention, can prepare a kind of A-type zeolite, this zeolite has very thin average initial particle size, the cation exchange property of the ability of excellent absorption oil and excellence and average very thin granularity.In addition, from relatively can finding out of embodiment 1-9 and embodiment 10-12 and embodiment 14 and 15, from the viewpoint of further improvement cation exchange property with the ability that absorbs oil, the present invention prepares first embodiment of fine zeolite particles method and the combination of second embodiment is preferred.From with relatively it can also be seen that of embodiment 14 and 15, from making the very thin viewpoint of average initial particle size, particularly preferably in advance the compound of alkaline including earth metal is joined in the silica source.
EXPERIMENTAL EXAMPLE
Adopt method described below, with each fine zeolite particles of preparation in embodiment 1 and 15, compare with the zeolite of preparation in the Comparative Examples 1, when determining in detergent composition to adopt fine zeolite particles on the impact of detergent composition detergency ability.
Preparation artificial contamination's cloth
To have artificial contamination's solution impregnation of following composition to cloth, with preparation artificial contamination's cloth.Employing is the photogravure roller applying device (gravure roll coater) of the Japanese Patent manufacturing of Hei 7-270395 according to publication number, and artificial contamination's solution is printed on the cloth, carries out artificial contamination's solution to the infiltration of cloth.Unit ability (cellcapacity) at the photogravure roller is 58cm
3/ cm
2, coating speed is 1.0m/min, drying temperature is 100 ℃, and time of drying be under the condition of 1min, carry out the process of artificial contamination's solution impregnation cloth, with the preparation artificial contamination cloth.As for cloth, adopt 2003
#Tprinted Fabrics (on market, can buy from Tanigashira Shoten company)
(composition of artificial contamination's solution)
Artificial contamination's solution composed as follows: lauric acid: 0.44%, tetradecanoic acid: 3.09%, pentadecylic acid: 2.31%, palmitinic acid: 6.18%, margaric acid: 0.44%, octadecanoic acid: 1.57%, oleic acid: 7.75%, triolein: 13.06%, palmitinic acid n-hexadecane ester: 2.18%, squalene: 6.53%, LCD product (on market, can buy from Wako Pure Chemical Industries company) from egg lecithin: 1.94%, the Kanuma red clay that is used for gardening: 8.11%, carbon black (on market, can buy from Asahi carbon company): 0.01%, and rest part is tap water.
Wash conditions and evaluation method
(composition of detergent composition)
The composition of every kind of detergent composition is as follows.Embodiment 1 or 15, or the fine zeolite particles of Comparative Examples 1: 25%, LAS-Na (straight chained alkyl sodium sulfonate) [is with LAS parent (NEOPELEXFS, on market, can buy from Kao company) be mixed with the aqueous sodium hydroxide solution of neutralizing agent one 48%]: 15%, Voranol EP 2001 [EMULGEN 108KM; The average mol of ethylene oxide (EO)=8.5, on market, can buy from Kao company]: 8%, yellow soda ash (DENSEASH, on market, can buy from central Glass Co., Ltd.): 15%, sodium sulfate (neutral anhydrous sodium sulphate, on market, can buy from Shikoku Kasei K.K.): 17%, S-WAT (S-WAT, on market, can buy from Mitsui Toatsu K.K.): 1%, sodium polyacrylate (molecular-weight average: 10000, on market, can buy from Kao company): 4%, crystalline silicate (SKS-6 can buy from Clariant-Tokuyama K.K. on market): 15%.
Prepare the clothes (underwear and full dress white shirt, its ratio are 7:3) of 2.2kg amount.Then with artificial contamination's cloth of 10 10cm * 10cm, be sewn on the carrier cotton of 3 35cm * 30cm, preparation is called the sample of " contaminated carrier cloth ".These clothes and contaminated carrier cloth are put into washing machine (" AISAIGO (registered trademark) NA-F70AP " equably, on market, can buy from Matsushita electrical equipment industry company limited), in washing machine, add the above-mentioned detergent composition of 20g, wash.Wash conditions is as follows:
Washing process: standard procedure;
The concentration of detergent composition: 0.067%;
Water hardness: 4 ° of DH;
The temperature of water: 10 ℃;
The ratio of the aqueous solution: 201/kg.
Before washing and after washing, adopt automatically record colorimeter (on market, can buy from Shimadzu company), measure uncontaminated cloth and the reflectivity that pollutes cloth at 550nm, determine detersive efficiency (%), get the mean value of 10 cloth.
As a result, comprise the detergent composition of embodiment 1 fine zeolite particles, detersive efficiency is 42%, comprises the detergent composition of embodiment 15 fine zeolite particles, and detersive efficiency is 48%.On the other hand, adopt the detergent composition of Comparative Examples 1 fine zeolite particles preparation, detersive efficiency is low to moderate 29%.Therefore find that comprise the detergent composition of embodiment 1 and 15 fine zeolite particles, detersive efficiency is higher than the detergent composition that comprises Comparative Examples 1 fine zeolite particles.As can be seen from these results, in detergent composition, when adopting the fine zeolite particles of method preparation of fine zeolite particles produced according to the present invention, the detersive efficiency of composition significantly improves.
Industrial usability
The method of fine zeolite particles produced according to the present invention, can effectively prepare the fine zeolite particles that comprises crystalline aluminosilicate, this fine zeolite particles, has very thin average initial particle size, the ability of excellent absorption oil and excellent cation exchange property, have very thin averageparticle granule degree, and good dispersing property.In addition, can also prepare a kind of detergent composition that comprises above-mentioned fine zeolite particles, this detergent composition has excellent detersive efficiency.
Equivalent
It will be understood by those skilled in the art that or adopt simple normal experiment just can find out, in this manual many Equivalents of described specific embodiments of the present invention.These Equivalents are also included within the scope of the present invention described in the following claim.
Claims (7)
1. method for preparing fine zeolite particles, it comprises and will react in aluminium source and/or silica source is sent into reactive tank is connected the circulation line, and the wet mixing device is configured to the part of described circulation line, make each raw material is added the slurries that form behind the described circulation line can to pass through circulation line;
Wherein aluminium source and/or silica source are fed in the circulation line that connects between reactive tank outlet and the described wet mixing device entrance,
Aluminium source and silica source are mixed in circulation line with blending ratio 0.5-2, and blending ratio is with SiO
2/ Al
2O
3Molar ratio represent.
2. according to claim 1 method wherein joins the aluminium source in the reactive tank, and circulates in circulation line; Silica source is joined in the circulation line.
3. according to claim 1 method wherein joins silica source in the reactive tank, and circulates in circulation line; The aluminium source is joined in the circulation line.
4. according to claim 1-3 each method, the wherein average initial particle size of fine zeolite particles≤1.5 μ m.
5. each method according to claim 1-3, wherein fine zeolite particles is the anhydrous form with following general formula:
xM
2O·ySiO
2·Al
2O
3·zMeO，
Wherein M is basic metal; Me is alkaline-earth metal; X is numeral, is 0.2-2; Y is numeral, is 0.5-6; With z be the numeral, be 0.005-0.1.
6. according to claim 1-3 each method, the wherein cationic exchange of fine zeolite particles speed 〉=150mg CaCO
3/ g.
7. detergent composition, it comprises the fine zeolite particles that can obtain by each method according to claim 1-6.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31860499A JP3611185B2 (en) | 1999-11-09 | 1999-11-09 | Method for producing fine particle zeolite |
| JP318604/1999 | 1999-11-09 | ||
| JP197076/2000 | 2000-06-29 | ||
| JP2000197076 | 2000-06-29 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008025797A Division CN1321889C (en) | 1999-11-09 | 2000-11-09 | Process for preparing fine zeolite particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101049944A CN101049944A (en) | 2007-10-10 |
| CN101049944B true CN101049944B (en) | 2013-01-16 |
Family
ID=18101002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710096813 Expired - Fee Related CN101049944B (en) | 1999-11-09 | 2000-11-09 | Process for preparing fine zeolite particles |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3611185B2 (en) |
| CN (1) | CN101049944B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4577862B2 (en) * | 2000-06-29 | 2010-11-10 | 花王株式会社 | Method for producing fine particle zeolite |
| JP6107359B2 (en) * | 2013-04-17 | 2017-04-05 | 東ソー株式会社 | Type A zeolite powder |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4385042A (en) * | 1979-08-06 | 1983-05-24 | Mobil Oil Corporation | Continuous reaction/separation method for nucleated growth reactions |
| EP0184244A1 (en) * | 1984-11-21 | 1986-06-11 | SOLVAY (Société Anonyme) | Process for the production of zeolites |
| US4661334A (en) * | 1983-09-21 | 1987-04-28 | Rhone-Poulenc Chimie De Base | Preparation of zeolites 4A and/or 13X |
| CN1045081A (en) * | 1989-02-23 | 1990-09-05 | 太原工业大学 | High silicon crystalline aluminosilicate and derivative thereof is synthetic in the non-aqueous system |
| EP0593014A1 (en) * | 1992-10-12 | 1994-04-20 | Kao Corporation | Nonionic powdery detergent composition |
-
1999
- 1999-11-09 JP JP31860499A patent/JP3611185B2/en not_active Expired - Fee Related
-
2000
- 2000-11-09 CN CN 200710096813 patent/CN101049944B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4385042A (en) * | 1979-08-06 | 1983-05-24 | Mobil Oil Corporation | Continuous reaction/separation method for nucleated growth reactions |
| US4661334A (en) * | 1983-09-21 | 1987-04-28 | Rhone-Poulenc Chimie De Base | Preparation of zeolites 4A and/or 13X |
| EP0184244A1 (en) * | 1984-11-21 | 1986-06-11 | SOLVAY (Société Anonyme) | Process for the production of zeolites |
| CN1045081A (en) * | 1989-02-23 | 1990-09-05 | 太原工业大学 | High silicon crystalline aluminosilicate and derivative thereof is synthetic in the non-aqueous system |
| EP0593014A1 (en) * | 1992-10-12 | 1994-04-20 | Kao Corporation | Nonionic powdery detergent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3611185B2 (en) | 2005-01-19 |
| JP2001139322A (en) | 2001-05-22 |
| CN101049944A (en) | 2007-10-10 |
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