CN104944430A - Novel technique for preparing high-purity montmorillonite by deeply purifying bentonite - Google Patents
Novel technique for preparing high-purity montmorillonite by deeply purifying bentonite Download PDFInfo
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Abstract
The invention discloses a novel technique for preparing high-purity montmorillonite by deeply purifying bentonite which does not contain cristobalite. According to the novel technique, impurity phases, particularly superfine quartz concomitant with montmorillonite in calcium bentonite can be effectively removed, and furthermore, the components and the structure of prepared high-purity montmorillonite are unchanged. According to the technological idea, firstly montmorillonite and impurity quartz particles are depolymerized by virtue of a certain mechanical force, so that the occurring states of montmorillonite and quartz are changed, and the binding force between montmorillonite and quartz is weakened; secondly, the dispersing difference between montmorillonite and quartz is expanded by virtue of a small amount of dispersing agent, so that the separation is relatively easy; finally, high-yield and high-purity montmorillonite is obtained by virtue of the dispersing difference between montmorillonite and quartz through centrifugal separation. The novel technique has the characteristics of simple process, mild conditions, low equipment requirement, high product additional value and the like.
Description
Technical field
The present invention relates to the separating and purifying method of montmorillonite, be specifically related to the method for separating-purifying montmorillonite from wilkinite, purification gained montmorillonite purity is high, and yield is high, and composition, structure are constant.
Background technology
Wilkinite take smectite type mineral as the rock of main ingredient, is that montmorillonite mineral reaches the clay and tonstein that can utilize content, have the good reputation of " omnipotent clay ".Wilkinite has wide range of applications, along with the development of modern science and technology, wilkinite is guided into nano material from fields such as traditional casting, pelletizing, drilling mud, sorbent materials, medicine, solid support material, fine chemistry industry be the high value added product of consumption target, comprised wilkinite intercalation compound, heat-storing material, gas filtration adsorption cleaning material, electro-conductive material, inorganic antiseptic, nano thickening rheological agent, the organic thickener rheology agent of nanometer, nano plastic, cosmetics additive, pharmaceutical carrier etc.High-purity montmorillonite is the basic substance of all high-grade montmorillonite product of preparation.In recent years, from wilkinite, the method for synthesis high-purity montmorillonite is very noticeable, becomes one of Domestic and foreign non metallic minerals thing investigation of materials focus.
China's bentonite ore, based on middle-low grade calcium-base bentonite, therefore, adopts physics wet-layer preparation high-purity montmorillonite product to be a general orientation.At present, the subject matter that Purification of Bentonite exists is: the first, because montmorillonite mineral crystal grain is thin, crystallization is poor, composition is changeable, and the impurity such as the superfine quartz of other granularities of association and cristobalite, its separating-purifying is very difficult, and particularly ca-montmorillonite is purified especially difficult.Second, the wilkinite that the industries such as medicine, foods and cosmetics adopt or montmorillonite (being generally calcium base soil) should not be purified with chemical method, also should not add the larger dispersion agent of toxicity in a large number, flocculation agent processes, in order to avoid the toxicant that chemical reagent is introduced is to the pollution of montmorillonite essence soil.3rd, while in chemical method purification process, cristobalite is dissoluted, montmorillonite also part is dissoluted, and affects the surface tissue of montmorillonite, silicon-oxy tetrahedron is distorted; And generate new reaction product (impurity) etc.
Summary of the invention
The present inventor is found by research, and that mainly exist in middle-low grade wilkinite and the difficult impurity removed is quartz and cristobalite.For the wilkinite not containing cristobalite, can by suitably grinding, then in bentonite suspension, the dispersion agents such as a small amount of such as Sodium hexametaphosphate 99 are added, fully stir and supersound process, high speed centrifugation can obtain high purity montmorillonite after being separated, and montmorillonite chemical composition and structure remain unchanged, effectively remove the quartzy impurity with montmorillonite association in calcium-base bentonite, thus complete the present invention.
The object of the present invention is to provide a kind of never containing the thinking of separating-purifying montmorillonite in the calcium-base bentonite of cristobalite, this thinking comprises the following steps:
(1) to the grinding that wilkinite raw ore carries out to a certain degree, the object of grinding changes quartz and the occurrence status of montmorillonite, makes it separate better;
(2) bentonite ore after grinding is made suspension, add appropriate dispersion agent, in conjunction with external influences such as stirring and supersound process, mineral grain is scatter well, meanwhile, expand the suspension otherness of quartz particles and montmorillonite particle;
(3) by the centrifugal force of suitable rotating speed, expand further and utilize suspension difference that is quartzy and montmorillonite, sharp separation quartz and montmorillonite, obtain high-purity montmorillonite at short notice.
Another object of the present invention is to provide a kind of never containing the method for separating-purifying montmorillonite in the calcium-base bentonite of cristobalite, the method comprises the following steps:
(1) wilkinite raw ore is placed in baking oven, abundant drying at least 8 hours at 60 DEG C, removes free water, make montmorillonite prevented from caking, obtain wilkinite to be ground;
(2) pulverizing grinding is carried out 60 minutes to wilkinite to be ground, dispersion agent is added in the aqeous suspension of the wilkinite raw ore after grinding, wherein in aqeous suspension, the mass ratio of montmorillonite and water is 1: 12, and dispersant dosage is the 0.8-1.2% of wilkinite quality;
(3) bentonite suspension after dispersion is fully stirred and supersound process through row, then low-speed centrifugal removing precipitated impurities, then high speed centrifugation collecting precipitation thing obtains purifying montmorillonite.
According to provided by the invention never containing the thinking of separating-purifying montmorillonite in the calcium-base bentonite of cristobalite, for the quartzy impurity with montmorillonite association, by grinding to a certain degree, effectively can change the occurrence status of quartz and montmorillonite, the quartz particles making to be attached to montmorillonite particle surface or be mixed in montmorillonite sheet interlayer is peeled away, and reduces agglomeration.Then appropriate dispersion agent is added by stirring and ultrasonicly carrying out vibration treatment, can quartzy and other impurity of disposable centrifugal segregation, obtain high purity montmorillonite.And because dispersant chemistry used is gentle, can not destroy montmorillonite composition and structure, its composition, structure remain unchanged.
Gained high purity montmorillonite can be directly used in the fields such as nano material, medicine, solid support material, fine chemistry industry, such as, be used as wilkinite intercalation compound, heat-storing material, gas filtration adsorption cleaning material, electro-conductive material, inorganic antiseptic, nano thickening rheological agent, the organic thickener rheology agent of nanometer, nano plastic, cosmetics additive and pharmaceutical carrier etc.
Accompanying drawing explanation
Fig. 1 illustrates the X ray diffracting spectrum of wilkinite raw ore in embodiment 1.
Fig. 2 illustrates the X ray diffracting spectrum of gained high-purity montmorillonite powder-product in embodiment 1.
Fig. 3 illustrates the transmission electron microscope collection of illustrative plates of wilkinite raw ore in embodiment 1.
Fig. 4 illustrates the transmission electron microscope collection of illustrative plates of wilkinite raw ore after grinding in embodiment 1.
Fig. 5 illustrates the transmission electron microscope collection of illustrative plates of gained high-purity montmorillonite powder-product in embodiment 1.
Fig. 6 illustrates the X ray diffracting spectrum of quartz/montmorillonite typical curve and quartz.
Fig. 7 illustrates the X ray diffracting spectrum contrast of a series of purification samples obtained under without milling time condition.
Fig. 8 illustrates the X ray diffracting spectrum contrast of a series of purification samples obtained under different centrifugal rotational speed condition.
Fig. 9 illustrates the schematic diagram of mechanism of the present invention.
Figure 10 illustrates the X ray diffracting spectrum of wilkinite raw ore and purification concentrate in comparative example 9.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.Described by these, the features and advantages of the invention will become more clear, clear and definite.
The invention provides a kind of not containing the thinking of the wilkinite deep purification method of cristobalite, this thinking comprises:
(1) to the grinding that wilkinite raw ore carries out to a certain degree, the object of grinding changes quartz and the occurrence status of montmorillonite, makes it separate better;
(2) bentonite ore after grinding is made suspension, add appropriate dispersion agent to expand the suspension difference of quartz particles and montmorillonite particle, in conjunction with external influences such as stirring and supersound process, quartz and montmorillonite particle are scatter well;
(3) by the centrifugal force of suitable rotating speed, expand further and utilize suspension difference that is quartzy and montmorillonite, sharp separation montmorillonite and impurity thing phase, obtain high-purity montmorillonite at short notice.
step (1)
The effect of thinking step (1) of the present invention is the occurrence status changing quartz and montmorillonite.
This step is a ring of most critical in thinking of the present invention, as there is many millimeters in the wilkinite of raw ore, pray for rice, nano level impurity particle, impurity and montmorillonite and the intergranular agglomeration of montmorillonite serious, be extremely unfavorable for the work that the degree of depth is purified.
Utilize disintegrating apparatus raw ore can be broken up, reduce agglomeration, make montmorillonite separate with impurity to a great extent, reduce and be attached on montmorillonite lamella or the quartz particles of sheet interlayer, provide good basis to the mask work in later stage.
In the method for the invention, pulverize degree of grind and need the very appropriate of control.Because the hardness ratio quartz of montmorillonite is little, so in process of lapping, montmorillonite is easier than quartz be ground into fine particle.Grind insufficient, montmorillonite can not separate well with quartz; It is excessive to grind, and quartz also becomes ultra-fine grain, reduces montmorillonite and the suspension difference of quartz on the contrary, is unfavorable for both separation.
In thinking of the present invention very important a bit, wilkinite has very strong water-absorbent, cohesiveness, and in process of lapping, moisture wilkinite easily adheres on wall of container or blade, is unfavorable for fully, evenly grinding.So will dry raw ore before the grinding, generally at 60 DEG C dry 8 hours, and the raw ore after drying not easily is exposed in moistening air for a long time, should carry out grinding steps at once.
step (2)
The effect of the step (2) of thinking of the present invention is that quartz and montmorillonite particle are scatter well in water.
In the method for the invention, as bentonitic aqeous suspension, its concentration is not particularly limited.But, in a preferred embodiment, the concentration of the aqeous suspension of montmorillonite is 5-10%, and this concentration is in the mass ratio of montmorillonite and water.The concentration of the aqeous suspension of preferred montmorillonite is 7-9% further.In this concentration range, can obtain highly purified montomorillonite, the excessive concentration or too low of montmorillonite aqeous suspension, the purity of gained montmorillonite declines.
The present inventor finds through research, ore pulp solid-to-liquid ratio affects the effect that the wilkinite degree of depth is purified within the specific limits, be mainly reflected on intergranular probability of collision, the particle of dispersion has certain kinetic energy and is suspended among ore pulp, they are among relative movement, if pulp density improves, the probability of collision between unit time endoparticle improves, just likely cause intergranular cohesion, and degree of scatter is declined.If pulp density is too low, then purification efficiency is not high, therefore, carries out dispersion treatment as far as possible, be conducive to the dispersion of particle under suitably low ore pulp solid-to-liquid ratio concentration, and then promotes that the degree of depth is purified, and improves the purity of montmorillonite.
In the method for the invention, as dispersion agent, use the dispersion agent of chemical property gentleness, as carbonate, phosphoric acid salt.When using the dispersion agent of other kinds, not only dispersion effect is poor, and the dispersion agent had also can cause composition, the structural modification of montmorillonite, is therefore not suitable for the present invention.
In the method for the invention, the effect of dispersion agent is the suspended dispersed sex differernce expanding montmorillonite and quartz.Wherein dispersant dosage is the 0.8-1.2% of wilkinite quality, is preferably about 1.0%.When dispersant dosage is within the scope of this, quartz can be made effectively to be separated with montmorillonite, when dispersant dosage higher than 1.2% time, difference suspension can be reduced on the contrary, when dispersant dosage lower than 0.8% time, because it causes dispersive ability not enough by quantity not sufficient.
The present inventor finds through research, and montmorillonite makes it electronegative because of lattice metalepsy, and again because of outstanding key peripheral zone positive electricity, in water medium, positive and negative charge attracts, and is partially formed " work " font structure, makes micropyromerides impurity by rest or be wrapped in wherein.After adding the dispersion agent proposed according to the present invention, acid ion is adsorbed on montmorillonite positive charge edge, makes montmorillonite become two negative electricity layer colloid, negative charge is higher, mutually repels each other, eliminates " work " font structure, micropyromerides impurity is made to lose rest, with montmorillonite particle separation.Along with the increase of dispersion agent massfraction, it is better that dispersion system degree of scatter becomes.But the excessive of dispersion agent adds, the current potential of electrostatic double layer can be declined because the concentration of negatively charged ion raises, thus cause the reunion of particle.
Under above-mentioned pulp density and dispersion agent proportioning, the mode combined with ultrasonic vibration treatment by mechanical stirring, can make montmorillonite fully be separated with quartz.
In a preferred embodiment, churning time is 4-20 hour, and more preferably 20 hours, stirring velocity was preferably 400r/min.
Within the scope of above-mentioned churning time and stirring velocity, higher dispersion efficiency can be realized.
In a preferred embodiment, ultrasonic (vibration) treatment time is 20-60 minute, and be preferably 30 minutes, ultrasonic vibration power is preferably more than 85%.
Within above-mentioned ultrasonic (vibration) treatment time and ultrasonic vibration power range, higher dispersion efficiency can be realized.
The present inventor finds through research, and the ca-montmorillonite of multilayer build-up produces lattice dilatation because of surface hydration, increase loose and partial solution between its particle crystal layer from, improve the zeta-potential absolute value of montmorillonite simultaneously; Water molecules is because of the surface energy of surface of clay, lattice negative charge effect, and the oxygen of lattice outer side and hydrogen-oxygen layer and water molecules form hydrogen bond, make the rapid aquation of montmorillonite, and then interlayer cation Ca
2+aquation enters in water, montmorillonite surface forms electrostatic double layer, double electrode layer repulsion impels montmorillonite basal spacing d (001) to expand, this one-phase can be called the surface hydration lattice dilatation stage of montmorillonite, add the zeta-potential absolute value that dispersion agent improves montmorillonite and quartz surfaces, montmorillonite basal spacing d (001) is expanded further, and quartz particles is dispersed into more small-particle; Add appropriate dispersion agent, in system, all particles institute is electrically charged electrically identical, is negative charge, makes montmorillonite particle end face-face, and eliminates because absorption that dead point graviational interaction produces is reunited with quartz particles; Compared with coalescent with face-face, it is weak that end-face combines, and can destroy by recurring structure when being subject to applied mechanical (ultrasonic vibration and stirring) shearing action, granular quartz loses rest, with montmorillonite particle separation, attenuates further, suspends.As shown in Figure 9.
But, above-mentioned mechanism is only infer the possibility of mechanism of the present invention, and the present invention is not limited to this.
step (3)
The impurity particles such as quartz are removed in the effect of the step (3) of thinking of the present invention.
In the method for the invention, centrifugal is make use of quartz and the suspension difference of montmorillonite equally, makes it separate rapidly at short notice.
Centrifuge speeds is preferably 600r/min-800r/min, more preferably from about 700r/min.Under this centrifugal speed, nearly all magazins' layout is in throw out, and most of montmorillonite remains in suspension, thus realize being separated of montmorillonite and quartz, if centrifugal speed is too high or too low, or be that montmorillonite purity is not good, that montmorillonite yield is not good, therefore not preferred.Finally with the rotating speed of 10000r/min, the montmorillonite in suspension is all isolated collection.
In a preferred implementation of the inventive method, the method comprises the following steps:
(1) to the grinding that wilkinite raw ore carries out to a certain degree, in the aqeous suspension of the wilkinite raw ore after grinding, add dispersion agent, wherein dispersant dosage is the 0.8-1.2% of wilkinite quality;
(2) fully stirred and supersound process, then centrifugation through row by the bentonite suspension after dispersion, collecting precipitation thing obtains purifying montmorillonite.
In further preferred implementation, the method comprises the following steps:
(1) pulverizing grinding is carried out 60 minutes to wilkinite to be ground, dispersion agent is added in the aqeous suspension of the wilkinite raw ore after grinding, wherein in aqeous suspension, the mass ratio of montmorillonite and water is 1: 12, and dispersant dosage is the 0.8-1.2% of wilkinite quality;
(2) by the bentonite suspension after dispersion through row magnetic agitation 20 hours and supersound process 30 minutes, then low-speed centrifugal removing precipitated impurities under 700r/min, then 10000r/min at a high speed under centrifugal collecting precipitate obtain purifying montmorillonite.
For the purifying montmorillonite obtained according to the inventive method, suitable aftertreatment can be carried out, as drying, grinding etc., so that application.
In a preferred embodiment, method of the present invention also comprises carries out pretreated step to wilkinite raw ore, and particularly, this pre-treatment step comprises:
(1) wilkinite raw ore is fully dry, remove free water, make montmorillonite prevented from caking, obtain wilkinite to be ground.
In a preferred embodiment, this pre-treatment step comprises:
(2) wilkinite raw ore is placed in baking oven, abundant drying at least 8 hours at 60 DEG C, removes free water, make montmorillonite prevented from caking, obtain wilkinite to be ground.
embodiment
The present invention is further described below by way of specific examples.
Embodiment 1
Wilkinite raw ore I (grade 65%) is put in an oven, abundant drying at least 8 hours at 60 DEG C, remove free water, make montmorillonite prevented from caking, obtain wilkinite to be ground.
Pulverizing grinding is carried out 60 minutes to wilkinite to be ground, sodium hexametaphosphate dispersant is added in the aqeous suspension of the wilkinite raw ore after grinding, wherein in aqeous suspension, the mass ratio of montmorillonite and water is 1: 12, and Sodium hexametaphosphate 99 consumption is 1.0% of wilkinite quality:
By the wilkinite I suspension after dispersion through row magnetic agitation 20 hours and supersound process 30 minutes, then low-speed centrifugal removing precipitated impurities under 700r/min, then 10000r/min at a high speed under centrifugal collecting precipitate obtain purifying montmorillonite.
Wherein, the X ray diffracting spectrum of wilkinite raw ore I as shown in Figure 1, the X ray diffracting spectrum of high-purity montmorillonite powder-product as shown in Figure 2, wilkinite raw ore, ground raw ore I, and the TEM collection of illustrative plates of purification concentrate is respectively as shown in Fig. 3, Fig. 4, Fig. 5.
From Fig. 1 and Fig. 2, dominant phase montmorillonite diffraction peak is d respectively
(001)=0.1519nm and 0.512nm, illustrates that they are ca-montmorillonite.Show in figure veil spacing be 0.33489nm be quartz characteristic diffraction peak; Veil spacing 0.312nm is the characteristic diffraction peak of feldspar; Veil spacing 0.303nm is the characteristic diffraction peak of calcite.
As shown in Figure 1, the major impurity of wilkinite raw ore I is quartz, and minor impurity is minute quantity feldspar and calcite, and the smectite content of raw ore is 65%.Through diffractogram andesine and the disappearance of calcite characteristic peak of the high-purity montmorillonite sample obtained of purifying, this shows, former state is purified through settling process and eliminated feldspar, calcite, the d of quartz in high-purity montmorillonite powder-product
(101)=0.3350nm diffraction peak intensity obviously reduces, the d of montmorillonite
(001)diffraction peak intensity relatively obviously strengthens, peak position remains unchanged (d
(001)=1.578nm), be still ca-montmorillonite.
The quartzy quantitation curves of gained high-purity montmorillonite powder-product as shown in Figure 6.As shown in Figure 6, the smectite content of high-purity montmorillonite powder-product is 96.5%, and yield is 70.1%.From Fig. 3, Fig. 4 and Fig. 5, in wilkinite raw ore I, quartz particles is state of aggregation, and the greater is formed by the particle aggregation of tens to several microns, and smaller is formed by several particles agglomerate to tens nanometers.Quartz assemble after aggregate granular size and montmorillonite granular size close, be usually dispersed in around montmorillonite or be present in a large number on montmorillonite lamella and between montmorillonite particle.In raw ore, the dispersiveness of montmorillonite and quartz is all bad, and a large amount of quartz particles is reunited and combined closely (Fig. 3) with montmorillonite; After suitable grinding, the dispersiveness of impurity and montmorillonite is significantly improved, and quartz particles exists with tiny particulate state substantially, and quartz and montmorillonite-base originally separate, and seldom assemble (Fig. 4); In concentrate after centrifugal purification, the content of quartz obviously reduces, only have granular quartz to be covered by the middle of curling montmorillonite lamella to be difficult to remove, in concentrate the aggregating state of montmorillonite also be improved significantly, exist mainly with platy shaped particle, seldom assemble (Fig. 5).
Comparative example 1
Test in the same manner as in Example 1, when difference is only to prepare bentonite suspension, do not add any dispersion agent.As shown in Figure 7, its purity is 90.7% to the X ray diffracting spectrum of gained purifying montmorillonite powder-product, and yield is 57.8%.
Comparative example 2
Test in the same manner as in Example 1, adding dispersant dosage when difference is only to prepare bentonite suspension is 0.5% of wilkinite quality.The X ray diffracting spectrum of gained purifying montmorillonite powder-product as shown in Figure 7 its purity is 95.23%, and yield is 69%.
Comparative example 3
Test in the same manner as in Example 1, adding dispersant dosage when difference is only to prepare bentonite suspension is 1.5% of wilkinite quality.As shown in Figure 7, its purity is 93.3% to the X ray diffracting spectrum of gained purifying montmorillonite powder-product, and yield is 70%.
Comparative example 4
Test in the same manner as in Example 1, adding dispersant dosage when difference is only to prepare bentonite suspension is 0.5% of wilkinite quality.As shown in Figure 7, its purity is 83.75% to the X ray diffracting spectrum of gained purifying montmorillonite powder-product, and yield is 73%.
In addition, when using a small amount of dispersion agent, the smectite structure change caused due to dispersion agent cationic is avoided.
Comparative example 5
Test in the same manner as in Example 1, difference is only low-speed centrifugal removing precipitated impurities under 500r/min.As shown in Figure 8, its purity is 90.5% to the X ray diffracting spectrum of gained purifying montmorillonite powder-product, and yield is 75%.
Comparative example 6
Test in the same manner as in Example 1, difference is only low-speed centrifugal removing precipitated impurities under 600r/min.As shown in Figure 8, its purity is 92% to the X ray diffracting spectrum of gained purifying montmorillonite powder-product, and yield is 73.2%.
Comparative example 7
Test in the same manner as in Example 1, difference is only low-speed centrifugal removing precipitated impurities under 800r/min.As shown in Figure 8, its purity is 96.7% to the X ray diffracting spectrum of gained purifying montmorillonite powder-product, and yield is 66%.
Comparative example 8
Test in the same manner as in Example 1, difference is only low-speed centrifugal removing precipitated impurities under 900r/min.As shown in Figure 8, its purity is 97.5% to the X ray diffracting spectrum of gained purifying montmorillonite powder-product, and yield is 48%.
Embodiment 2
Wilkinite raw ore I is put in an oven, abundant drying at least 8 hours at 60 DEG C, remove free water, make montmorillonite prevented from caking, obtain wilkinite to be ground.
Carry out pulverizing grinding 30 minutes to wilkinite to be ground, in the aqeous suspension of the wilkinite raw ore after grinding, add sodium hexametaphosphate dispersant, wherein in aqeous suspension, the mass ratio of montmorillonite and water is 1: 12, and dispersant dosage is 1.0% of wilkinite quality;
By the wilkinite I suspension after dispersion through row magnetic agitation 20 hours and supersound process 30 minutes, then low-speed centrifugal removing precipitated impurities under 700r/min, then 10000r/min at a high speed under centrifugal collecting precipitate obtain purifying montmorillonite.
Similar shown in the X ray diffracting spectrum of gained high-purity montmorillonite powder-product and Fig. 2, its purity is 93.7%, and yield is 63%.
Embodiment 3
Wilkinite raw ore I is put in an oven, abundant drying at least 8 hours at 60 DEG C, remove free water, make montmorillonite prevented from caking, obtain wilkinite to be ground.
Carry out pulverizing grinding 45 minutes to wilkinite to be ground, in the aqeous suspension of the wilkinite raw ore after grinding, add sodium hexametaphosphate dispersant, wherein in aqeous suspension, the mass ratio of montmorillonite and water is 1: 12, and dispersant dosage is 1.0% of wilkinite quality;
By the bentonite suspension after dispersion through row magnetic agitation 20 hours and supersound process 30 minutes, then low-speed centrifugal removing precipitated impurities under 700r/min, then 10000r/min at a high speed under centrifugal collecting precipitate obtain purifying montmorillonite.
Similar shown in the X ray diffracting spectrum of gained high-purity montmorillonite powder-product and Fig. 2, its purity is 94.7%, and yield is 65.3%.
Embodiment 4
Wilkinite raw ore I is put in an oven, abundant drying at least 8 hours at 60 DEG C, remove free water, make montmorillonite prevented from caking, obtain wilkinite to be ground.
Carry out pulverizing grinding 75 minutes to wilkinite to be ground, in the aqeous suspension of the wilkinite raw ore after grinding, add sodium hexametaphosphate dispersant, wherein in aqeous suspension, the mass ratio of montmorillonite and water is 1: 12, and dispersant dosage is 1.0% of wilkinite quality;
By the bentonite suspension after dispersion through row magnetic agitation 20 hours and supersound process 30 minutes, then low-speed centrifugal removing precipitated impurities under 700r/min, then 10000r/min at a high speed under centrifugal collecting precipitate obtain purifying montmorillonite.
Similar shown in the X ray diffracting spectrum of gained high-purity montmorillonite powder-product and Fig. 2, its purity is 94%, and yield is 73%.
As shown in Figure 7, when within 60 minutes, increasing from 30 points of clockwise upon grinding, in the sample that purification obtains, smectite content increases gradually, and yield is also in increase simultaneously; But continue to extend milling time, the yield of montmorillonite continues to increase, and purity reduces on the contrary.This is because if grind insufficient, montmorillonite and quartz can not scatter well; If it is excessive to grind, quartz makes to become ultra-fine grain, reduces montmorillonite and the suspension difference of quartz on the contrary, is unfavorable for that the sedimentation of quartz is removed.
As shown in Figure 8, when centrifugal speed increases from 500r/min to 900r/min, in gained purification sample, the content of montmorillonite increases gradually, and yield reduces to some extent.The purity of montmorillonite is higher, and yield is also lower.This is because the quartz of same granular size is more great than the ratio of montmorillonite, and quartz is dispersed into particle in suspension, improve centrifugal speed, in the centrifugation obtained, the content of quartz increases, and in the suspension of upper strata, the purity of montmorillonite improves.
Consider quartzy dispersion effect and montmorillonite dispersion effect in system, and the purity of montmorillonite and yield in gained purification sample, 700r/min centrifugal speed is more suitably.
Comparative example 9
Test in the same manner as in Example 1, difference is only that using another kind of bentonite ore II instead carries out purification experiment as raw ore.The X ray diffracting spectrum of raw ore II and gained purifying montmorillonite powder-product as shown in Figure 10.
The phase of dominant shown in Figure 10 montmorillonite diffraction peak is d (001)=0.1497nm and 0.500nm respectively, is similarly typical calcium-base bentonite, and to show veil spacing in figure be 0.32489nm is the characteristic diffraction peak of quartz; The characteristic diffraction peak of the feldspar that veil spacing 0.315nm is; Veil spacing 0.301nm is the characteristic diffraction peak of calcite.Smectite content 44% in raw ore, the purity after the method is purified is promoted to 95%, yield 72%.
experimental example
quartz quantitation curves is measured
X-ray diffraction test is carried out by different mass than the standard model of preparation one group of known quartz content, by the strongest diffraction peak (d of alpha-quartz in the X ray diffracting spectrum of each sample with pure alpha-quartz and pure ca-montmorillonite
101=0.335nm) integrated intensity and the integrated intensity of same diffraction peak of pure alpha-quartz standard specimen be divided by, obtain one group of relative intensity numerical value.Take relative intensity value as X-axis, alpha-quartz massfraction is Y-axis, to carrying out quadratic polynomial regression fit a little, obtains cristobalite quantitation curves figure.The regression equation of working curve is:
Y=0.00616+0.75252X+0.22834X
2
Wherein, X
2represent the strongest diffraction peak (d of α-cristobalite in the X ray diffracting spectrum of each sample
101=0.335nm) integrated intensity and the ratio of integrated intensity of same diffraction peak of pure alpha-quartz standard specimen, i.e. relative intensity value;
Linearly dependent coefficient R
2=0.999.
When only containing alpha-quartz impurity in wilkinite sample, in this sample, the percentage composition of montmorillonite is 1-Y.
industrial applicibility
The present invention is disperseed by ultra-fine grain, make montmorillonite and the depolymerization of ultra-fine impurity quartz particles, improve the dispersion suspension performance of montmorillonite and quartz particles, utilize fractional centrifugation to remove quartz simultaneously, and obtain high-purity montmorillonite, to solve in Montmorillonite Purification the technical barrier that quartz is difficult to remove, have that process is simple, mild condition equipment requirements is low and added value of product high.
More than in conjunction with embodiment and preferred embodiment, concrete grammar of the present invention and technical thought have been described in detail, but these descriptions do not form limitation of the scope of the invention.Should be appreciated that when not departing from the scope of the invention and spirit, can carry out multiple modification, improvement and replacement to concrete grammar of the present invention and technical thought, these modifications, improvement and replacement all should fall in the protection domain of appended claims.
Claims (11)
1., not contain the wilkinite of cristobalite for a raw material, the technology of degree of depth synthesis high-purity montmorillonite, this technology comprises the following steps:
(1) to the grinding that wilkinite raw ore carries out to a certain degree, in the aqeous suspension of the wilkinite raw ore after grinding, add a small amount of dispersion agent, wherein dispersant dosage is the 0.8-1.2% of wilkinite quality;
(2) fully stirred and supersound process, then centrifugation through row by the bentonite suspension after dispersion, collecting precipitation thing obtains purifying montmorillonite.
2. do not purify containing the wilkinite degree of depth of cristobalite for one kind, prepare the technical thought of high-purity montmorillonite: by mechanical force to a certain degree, make montmorillonite and the depolymerization of ultra-fine impurity quartz particles, change montmorillonite and the occurrence status of quartz, weaken montmorillonite and quartzy bonding force; Suitable dispersion treatment is carried out to wilkinite, expands the poor dispersion opposite sex of montmorillonite and quartz, make it more easily separated; Utilize the poor dispersion opposite sex of montmorillonite and quartz, high speed centrifugation makes its sharp separation; Obtain high yield pulp1 and highly purified montmorillonite.
3. method according to claim 1, wherein, described grinding plant can be Universalpulverizer, ball mill, super grinder, vibration mill, machine for cutting charge into pieces etc.
4. method according to claim 1, wherein, described dispersion agent is selected from sodium carbonate, sodium-chlor, salt of wormwood and Sodium hexametaphosphate 99, preferred Sodium hexametaphosphate 99.
5. method according to claim 1, wherein, described churning time 4-20 hour, ultrasonic disperse 30-60 minute.
6. method according to claim 1, wherein, in step (1), the Universalpulverizer grinding raw ore time is 30-80 minute, preferred milling time is 60 minutes: and/or the concentration of the aqeous suspension of montmorillonite to be purified is 5-10%, this concentration is in the mass ratio of montmorillonite and water, and the concentration of the aqeous suspension of preferred montmorillonite is 7-9%; And/or dispersant dosage is 1.0% of wilkinite quality.
7. method according to claim 1, wherein, in step (2),
Churning time is 4-20 hour, and stirring velocity is preferably 400r/min; And/or the ultrasonic vibration treatment time is 30-60 minute, ultrasonic vibration power is more than 85%; And/or
Centrifuge speeds is 700r/min, removes precipitation, and be separated with 10000r/min centrifugation upper suspension, collecting precipitation thing obtains purifying montmorillonite again.
8. the method according to any one of claim 1-3, the method comprises the following steps:
(1) to the grinding that wilkinite raw ore carries out to a certain degree, the wilkinite after grinding is made aqeous suspension, and in suspension, add dispersion agent, wherein dispersant dosage is 1.0% of wilkinite quality;
(2) by above-mentioned aqeous suspension magnetic agitation after 20 hours, supersound process 30 minutes, then centrifugation, collecting precipitation thing obtains purifying montmorillonite.
9. the method according to any one of claim 1-3, the method comprises the following steps:
(1) with Universalpulverizer, pulverizing grinding is carried out 60 minutes to wilkinite to be ground, dispersion agent is added in the aqeous suspension of the wilkinite raw ore after grinding, wherein in aqeous suspension, the mass ratio of montmorillonite and water is 1: 12, and dispersant dosage is the 0.8-1.2% of wilkinite quality; Grind 60 minutes, the wilkinite after grinding is made aqeous suspension, and wherein the mass ratio of montmorillonite and water is 1: 12, in suspension, add dispersion agent, and wherein dispersant dosage is 1.0% of wilkinite quality;
(2) stir 20 hours under 400r/min stirring velocity, then with 90% ultrasonic vibration power, supersound process 30min, initial centrifugation under 700r/min centrifugal speed, remove precipitated impurities, under 10000r/min speed, centrifugation is carried out to the suspension that initial centrifugation obtains, obtain final purifying montmorillonite.
10. the method according to any one of claim 1-7, the method is further comprising the steps of before step (1):
Wilkinite raw ore is fully dry, remove free water, make montmorillonite prevented from caking, obtain wilkinite to be ground.
11. methods according to Claim 8 described in any one, wherein, further comprising the steps of before step (1):
Wilkinite raw ore is placed in baking oven, abundant drying at least 8 hours at 60 DEG C, removes free water, make montmorillonite prevented from caking, obtain wilkinite to be ground.
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| CN106281044A (en) * | 2016-08-09 | 2017-01-04 | 西安博尔新材料有限责任公司 | A kind of preparation method of floating type aqueous polishing liquid |
| CN106745014A (en) * | 2017-01-24 | 2017-05-31 | 湘潭大学 | A kind of method of purification of low taste sepiolite |
| CN107324351A (en) * | 2017-07-06 | 2017-11-07 | 四川维奥制药有限公司 | A kind of medicinal smectite and its preparation technology |
| CN107814388A (en) * | 2016-09-12 | 2018-03-20 | 先声药业有限公司 | A kind of preparation method of montmorillonite |
| CN109794217A (en) * | 2019-01-30 | 2019-05-24 | 中国地质大学（武汉） | A kind of phosphoric acid removing na-montmorillonite ultrathin nanometer piece and preparation method thereof |
| CN113683095A (en) * | 2021-09-26 | 2021-11-23 | 苏州中材非金属矿工业设计研究院有限公司 | Method for purifying natural sodium bentonite containing cristobalite |
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| CN106281044A (en) * | 2016-08-09 | 2017-01-04 | 西安博尔新材料有限责任公司 | A kind of preparation method of floating type aqueous polishing liquid |
| CN107814388A (en) * | 2016-09-12 | 2018-03-20 | 先声药业有限公司 | A kind of preparation method of montmorillonite |
| CN106745014A (en) * | 2017-01-24 | 2017-05-31 | 湘潭大学 | A kind of method of purification of low taste sepiolite |
| CN107324351A (en) * | 2017-07-06 | 2017-11-07 | 四川维奥制药有限公司 | A kind of medicinal smectite and its preparation technology |
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| CN109794217A (en) * | 2019-01-30 | 2019-05-24 | 中国地质大学（武汉） | A kind of phosphoric acid removing na-montmorillonite ultrathin nanometer piece and preparation method thereof |
| CN109794217B (en) * | 2019-01-30 | 2020-10-30 | 中国地质大学（武汉） | Phosphoric acid stripping sodium-based montmorillonite ultrathin nanosheet and preparation method thereof |
| WO2022160507A1 (en) * | 2021-01-29 | 2022-08-04 | 海南海力制药有限公司 | Method for purifying montmorillonite, diosmectite, and preparation method therefor |
| CN113683095A (en) * | 2021-09-26 | 2021-11-23 | 苏州中材非金属矿工业设计研究院有限公司 | Method for purifying natural sodium bentonite containing cristobalite |
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