CN1157260A - Macropore amplifying spherical silica-gel and its manufacturing method - Google Patents
Macropore amplifying spherical silica-gel and its manufacturing method Download PDFInfo
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- CN1157260A CN1157260A CN 96122871 CN96122871A CN1157260A CN 1157260 A CN1157260 A CN 1157260A CN 96122871 CN96122871 CN 96122871 CN 96122871 A CN96122871 A CN 96122871A CN 1157260 A CN1157260 A CN 1157260A
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Abstract
The invention provides a spherical silica gel and process for preparation thereof. The spherical silica gel having remarkably increased macropores, remarkably improved water crushing resistance, improved resistance to temperature and pressure changes and remarkably increased rates of absorption and desorption. Accoring to the process for preparation of the spherical silica gel, when an alkali silicate solution is instantaneously mixed with a mineral acid and the resultant solution is discharged into a gaseous medium to produce spherical silica gel. In such a process for preparation, it is characterised in that water-insoluble solid particles are dispersed in at least one of the alkali silicate solution and the mineral acid. So the solid particles can perform as a macropores accelerant.
Description
The present invention relates to a kind of macropore increases and water-fast crushing performance improves spherical silica-gel and manufacture method thereof.Prior art
Spherical silica-gel is widely used in the carrier of the various sorbent materials that comprise siccative, various support of the catalyst and other medicine etc.
Manufacture method as spherical silica-gel, known have: the water-sol of silicon-dioxide is suspended in the liquid solvent of lam-oil etc., and at solidified method in suspension (special public clear 26-4113 communique), with with the alkali silicate aqueous solution and acid together, import from each introducing port simultaneously and have in the container of discharge outlet, can in 1.2 seconds, generate gelation, be converted into the silicon sol that concentration is 130-173g/l, pH6-10.5, be thrown in the gas-solvent with being about to this colloidal sol, obtain the method (special public clear 48-13834 communique) of spherical silica-gel etc.
Though known silica gel can satisfy the purposes as siccative, sorbent material haply, its existing problem is: broken easily when it contacts with water, and when being used in the adsorption unit of PSA type, its endurance quality for temperature variation and pressure change is not enough; In addition, the speed of its absorption, desorb is also not enough.
According to present inventors' research, silica gel in the past, its micropore, mesopore as absorption or reactive site is all bigger, and the content of macropore is less, this can be considered to the reason place of the problems referred to above.
Present inventors find: alkali silicate solution and mineral acid are done instantaneous mixing, make it form colloidal sol, again the colloidal sol that forms is discharged in gas-solvent, to form colloid, at this moment, if the water-insoluble solid particle is scattered among at least a in alkali silicate solution or the first machine acid, then described solids can play the effect of macropore promotor, can increase the macropore (aperture) of spherical silica-gel significantly.In addition, present inventors also find, with this spherical silica-gel, can improve the water-fast crumbliness of colloidal significantly, improve the weather resistance to temperature variation, pressure change, and the speed of its absorption, desorb also improves significantly.
That is, the objective of the invention is to, a kind of spherical silica-gel and manufacture method thereof are provided, described spherical silica-gel, its macropore (aperture) increases significantly, can improve water-fast crumbliness significantly, raising is to the weather resistance of temperature variation, pressure change, and the speed of its absorption, desorb also improves significantly.
According to the present invention, a kind of like this manufacture method of spherical silica-gel is provided, alkali silicate solution and mineral acid are done instantaneous mixing, make it form colloidal sol, the colloidal sol that forms is discharged in gas-solvent, form colloid again, form spherical silica-gel thus.It is characterized in that in such manufacture method, the water-insoluble solid particle is scattered among at least a in alkali silicate solution or the mineral acid, then described solids can play the effect of macropore promotor.
According to the present invention, a kind of like this spherical silica-gel also is provided, it is characterized in that described spherical silica-gel is made up of the matrix of silica gel and the water-insoluble solid particle as macropore promotor that is scattered in this silica matrix; SiO in this matrix
2And solids (SP) are with 95: 5-55: 45 weight ratio exists; And have with mercury penetration method micropore volume measured, 0.08ml/g and water-fast crumbliness in the scope of the pore radius of 7.5-7500nm.
Alkali silicate solution and mineral acid are being done instantaneous mixing, make it form colloidal sol, the colloidal sol that forms being discharged forms on the colloid this point in gas-solvent again, manufacture method of the present invention and technology in the past do not have any difference, but, the water-insoluble solid particle is scattered among at least a in alkali silicate solution or the mineral acid as macropore promotor, then is feature of the present invention.
That is,, the water-insoluble solid particle is scattered in wherein in advance, under this state, carries out reaction, generate silicon sol and gel, can increase the macropore (aperture) of the spherical silica-gel of gained significantly by alkali silicate and mineral acid no matter be alkali silicate or mineral acid.
Accompanying drawing Fig. 1 just is scattered in the solution in the alkali silicate and the spherical silica-gel of inorganic acid reaction gained by aluminium hydroxide, and, mark and draw the relation (concrete) that has shown with the pore radius and the micropore volume of mercury penetration method gained among the figure with reference to following example by the not alkali silicate of fusion aluminium hydroxide and the spherical silica-gel of mineral acid gained.Can see that according to The above results, the spherical silica-gel of the alkali silicate gained of fusion aluminium hydroxide is not common spherical silica-gel yet, has the macropore of its pore radius more than 10nm hardly; By contrast, mixed the spherical silica-gel of aluminium hydroxide, then along with the increase of its blended amount, its macropore increases significantly.
In addition, Fig. 2 is just by alkali silicate solution and the spherical silica-gel that is dispersed with the inorganic acid reaction gained of amorphous silica powder, and by alkali silicate and not fusion the spherical silica-gel of the mineral acid gained of amorphous silica is arranged, illustrate relation (the following example of concrete reference) with the pore radius and the micropore volume of mercury penetration method gained.Can see, according to above-mentioned result, the spherical silica-gel of the mineral acid of fusion amorphous silica and alkali silicate gained not, it also is common spherical silica-gel, have the macropore of its pore radius more than 10nm hardly, by contrast, mixed the spherical silica-gel of amorphous silica, then along with the increase of its blended amount, its macropore diameter increases significantly.
A notable attribute of spherical silica-gel of the present invention is, described silica gel have with mercury penetration method, pore radius in the 10-7500nm scope more than the measured 0.08ml/g, particularly, the micropore volume of 0.1ml/g.
Spherical silica-gel of the present invention is along with its macropore enlarges markedly, and its water-fast crumbliness also is significantly improved.That is, shown in following embodiment, when the volume of its macropore was lower than 0.06ml/g, the broken number when then this spherical silica-gel contacts with water reached (comparative example 1) more than 60%.By contrast, according to the present invention, even then the volume of this its macropore of spherical silica-gel is in above-mentioned scope, the broken number when this spherical silica-gel contacts with water also can be controlled in (embodiment 1) below 1%.
Silica gel contacts broken reason and can think with water: because heat of adsorption rises temperature, cause the colloid thermal expansion, colloid is broken because of not resisting this caused distortion of expanding.Yet, in spherocolloids of the present invention, can think that its inner macropore can relax described distortion, thereby prevents fragmentation.
For the temperature variation in the PSA device, pressure change, above-mentioned macropore also can play the effect that relaxes the corresponding distortion that produces owing to described variation, therefore, can improve the weather resistance of spherical silica-gel significantly, prolong the life-span that it uses as siccative, sorbent material, carrier etc. greatly.
Again, being determined during in absorption, desorb of silica gel, and in spherical silica-gel of the present invention from the diffusion position to the speed of the diffusion of reactive site, because of wherein macropore spreads easily, therefore, it adsorbs, the speed during desorb is also significantly improved.
In the present invention, owing to the existence of water-insoluble solid particle causes the macropore of spherical silica-gel to be able to cause of increased, can think: solids are to gather materials or the form of spacer is present in the colloidal sol and colloid of silicon-dioxide, it has just formed the space in colloidal stroma when finally forming colloid.
For this reason, as solids, so long as water-fast, have avidity (affinity) for aqueous solvent, and be stable can using, therefore, can use inorganic or organic solids widely, but, generally with inorganic be ideal.
Solids can be scattered in the alkali silicate solution, also can be scattered in the mineral acid, alkali stable solids can be added in the alkali silicate, on the other hand, also can will add in the mineral acid the stable solids of acid.
The median size of solids it is desirable to use the particle with 4-10 μ m median size especially usually at 0.1-15 μ m.If the median size of solids is less than above-mentioned particle diameter, then the degree of macropore increase reduces; Again, greater than above-mentioned particle diameter, then colloidal intensity reduces as the median size of solids, and two kinds of situations are all undesirable.
The consumption of solids (SP) is preferably as follows: with the silicon-dioxide (SiO in the alkali silicate
2) be the benchmark meter, SiO
2: SP=95: 5 to 55: 45 weight ratio; Good especially is 85: 15 to 70: 30 weight ratio.Less than above-mentioned scope, then the degree that increases of macropore reduces as the amount of solids; Again, greater than above-mentioned scope, then colloidal intensity reduces as its amount, and adsorption activity also reduces, so either way undesirable.
In addition, the alkali silicate solution or the mineral acid that are dispersed with solids should have the following viscosity of 20 centipoises, and greater than above-mentioned viscosity, it is very difficult then will mixing in the extremely short time and do to mix uniformly as viscosity.
As above said, according to the present invention, can obtain macropore (aperture) and enlarge markedly, the spherical silica-gel that water-fast crushing performance is also improved significantly, the speed when its endurance quality raising for temperature variation, pressure change, absorption, desorb also obviously improves.Simultaneously, the method that is used for solids being scattered in alkali silicate or mineral acid of its necessity also has such advantage: manufacture method is easy, can make spherical silica-gel efficiently with less operation.The optimal morphology (alkali silicate) of invention
Can use the alkali silicate of composition, particularly as alkali silicate, use the aqueous solution of this water glass with formula (1):
Na
2O·mSiO
2 ……(1)
In the formula, m is the integer of 1-4, particularly, is the integer of 2.5-3.5.
The production rate of the composition of above-mentioned alkali silicate and the stability of colloidal sol, particle and the particle diameter of particle have relation.If, SiO
2Mol ratio (m) less than above-mentioned scope, then the particle yield is low, perhaps the form of the shape of particle and particle is easily inconsistent; Perhaps, desiring to reach the part neutralization needs excessive acid, thereby undesirable.On the other hand, as SiO
2Mol ratio (m) greater than above-mentioned scope, the poor stability of colloidal sol then, adsorption activity reduces, perhaps the particle shape stray circle is spherical, perhaps presents size distribution and crosses steep grade and be not suitable for situation.
The concentration of alkali silicate is with SiO
2Be the benchmark meter, the concentration of 100-225g/l preferably, good especially is the concentration of 130-150g/l.
As acid, can use various mineral acids and organic acid, but, be preferably the mineral acid that uses as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc. from economic point of view.Wherein, considering the equal first-class requirement of performance, particle diameter and the form of spherical silica-gel, is best with sulfuric acid.
In order to carry out the reaction of homogeneous, can use the dilute aqueous solution of acid, typically use the weaker concn of the 1-15% (weight) of acid.(solids)
As solids, so long as water-fast, have avidity (affinity) for aqueous solvent, and be stable can using, can be extensive use of inorganic or organic solids, but, generally with inorganic be ideal.
As inorganic solids, can enumerate oxide compound, composite oxides, oxyhydroxide or the complex hydroxide of the element of periodic table of elements group III A, IVA family, IVB family, VB family or group VIII.Particularly, can enumerate aluminum oxide, silicon-dioxide, titanium oxide, zirconium white, vanadium oxide, niobium oxides, chromic oxide, molybdenum oxide, Tungsten oxide 99.999, ferric oxide, cobalt oxide, nickel oxide, palladous oxide, platinum oxide, zirconium silicate etc.
Wherein, be preferably silicon-dioxide, aluminum oxide, titanium oxide or zirconium white, good especially is, can use amorphous silicon-dioxide effectively as silicon-dioxide, can use the specific surface area of the aluminium hydroxide of gibbsite class, false boehmite type alumina gel etc. at 50m as aluminum oxide
2The oxide compound that/g is above.
Again,, can use, particularly, can use natural or synthetic clay or zeolite as frame shape aluminosilicate or layer aluminosilicate as first machine solids.As clay mineral, can enumerate and to take off stone, beidellite, nontronite, saponite, hectorite, sauconite, dust falling rocks, pyrophyllite, kaolinite, lobate serpentine, sepiolite, polygorskite, vermiculite etc.As zeolite, can enumerate all kinds of zeolites as A type, X type, Y type, P type, mordenite, silica, GS5 etc.In addition, also can use the acid treatment thing and the calcining matter of above-mentioned mineral.Have again,, can use gac as solids.The median size of solids of the present invention is 0.1-15 μ m, it is desirable to especially, uses the particle of the median size with 4-10 μ m.(preparation of stock liquid)
Solids can be scattered in the solution of alkali silicate, also can be scattered in the mineral acid.Can add alkali stable solids to described solution, for example, aluminium hydroxide can be added in the alkali silicate; On the other hand, also can add, for example, amorphous silica can be added in the mineral acid stable solids.
The consumption of solids (SP) is preferably as follows: with the silicon-dioxide (SiO in the alkali silicate
2) be the benchmark meter, SiO
2: SP=95: 5 to 55: 45 weight ratio, good especially is 85: 15 to 70: 30 weight ratio.
In addition, be dispersed with the alkali silicate solution of solids or first machine acid and should have the following viscosity of 20 centipoises,, then can in the extremely short time, mix and be uniform mixed base silicate and mineral acid by this viscosity is maintained at above-mentioned scope.(manufacturing of silica gel)
According to the present invention, alkali silicate and the mineral acid made as mentioned above, one of make an addition in its two to major general's solids are supplied to one two fluidic nozzle, and the two does instantaneous mixing to make it, forms colloidal sol, then be thrown in the gas-solvent, make its gelation.
Supply with the alkali silicate of second fluid nozzle and the supply ratio of mineral acid, the pH when it is mixed becomes 6-11; In addition, the ratio of its flow can have multiple variation, but it is desirable to, and its flow rate ratio is 70: 30-50: 50 scope.
Can use the nozzle with inner barrel and outer cylinder body as second fluid nozzle, the front end of cylindrical shell has mixing portion within it, and has ejiction opening at the front end of mixing portion.Can have a kind of fluidic passage of supply on the inner barrel in the described nozzle, and the annulus between inner barrel and outer cylinder body can have another fluidic passage.When fluid was conducted to inner barrel and annulus, fluid imported along its tangential direction, and the eddy flow of generation can make the instantaneous possibility that is mixed into, and therefore, this is the ideal structure.If two fluidic backflow directions are opposite mutually, then best.Generally, though unnecessary, also can be contained as the public clear 48-13834 communique of spy, and the turning vane that eddy flow is used takes place in design.
The silicon dioxide gel that sprays from second fluid nozzle keeps the form of drop to carry out gelation in gas-solvent, becomes the globular silicon dioxide colloid.Can also can become descending coniformly along any direction from the water-sol of nozzle ejection; Perhaps, also can do to make progress or horizontal ejection.
Falling on the direction of silica hydrosol, preferably be provided with the storagetank of the silica hydrosol of receivability aqueous solvent.And, preferably can in this storagetank, carry out the aging and dealkalize of silicon-dioxide solvent.
Usually, can in receiver, pour skim into, like this, can reclaim on broken silica hydrosol ground dilute alkaline aqueous solution; Simultaneously, by it is worn out, obtain the silica gel of performance and dimensionally stable.This burin-in process should be handled 4-16 hour under 40-15 ℃ temperature.
The silicon dioxide gel that burin-in process finishes in order to remove the alkali branch that residues in the colloid, can carry out dealkalize by acid treatment.Described dealkalize should be used the aqueous acid of pH1-3.5, handles under 40-15 ℃ temperature 8-24 hour.
The above-mentioned silica gel that disposes remakes clean.Clean is used flowing water, and its pH is in the scope of 7.5+0.1, and its electric conductivity should be in the 50mS scope.
At last, with resulting silica dehydrator, make the xerogel of silicon-dioxide.Described drying is preferably under 80-200 ℃ the temperature, carries out 12-48 hour.Drying also can be carried out so-called steam drying when water vapour is arranged.(silica gel)
From its end-use, silica gel of the present invention usually with the particle diameter of 1-6mm for well, especially, be better with median size with 2-5mm.
That above-mentioned silica gel preferably has is measured in the scope of the pore radius of 10-7500nm with mercury penetration method, more than the 0.08ml/g, the micropore volume of 0.09-0.15ml/g particularly, all micropore volumes should be in the scope of 1.19cc/g-25cc/g.
In addition, its specific surface area can be at 250-650m
2/ g, good especially is, can be at 500-600m
2The scope of/g.Spherical silica-gel of the present invention has alleviated weight because of containing a large amount of macropores, and its volume density is in the scope of 0.08-0.35g/ml.
More than, with embodiment the present invention is described.
Below, with regard to of the present invention contain macropore promotor (hereinafter referred to as SP), have the manufacture method and the rerum natura thereof of the spherical silica-gel of water-fast crumbliness and a large amount of macropores, be illustrated for example.In addition, among the present invention, the measurement of various rerum naturas is carried out according to method as described below.
(1) specific surface area
Use the Sortomatic Series 1800 of カ Le ロ ェ Le バ corporate system, measure according to the BET method.
(2) micropore volume-1
Same with (1), according to Sortomatic Series 1800, the BJH method is measured.
(3) micropore volume-2
To try to achieve the micropore volume in the aperture that is in 7.5-7500nm at 3 hours sample 0.5g of 150 ℃ of dryings with the PORE SIZE APPARATUS FOR (マ Network ロ メ リ is in Network ス corporate system オ-ト Port ア 9220) of mercury penetration method.
(4) tamped density
With pack into the graduated cylinder of 500ml of sample 200g, be vibrated to an interior sample volume and do not change, read capacity.Again this sample was descended dry 2 hours at 150 ℃, survey its moisture, try to achieve the g/ml of anhydrous conversion.
(5) compressive strength
The load sensor of on the desk-top load determinator of ア イ コ engineering corporation system the 50kgf capacity being installed is measured.Again, loaded speed is 5mm/min, and the load when sample destroys reads with numeric representation.
(6) viscosity
Use Brookfield viscometer (the Tokyo metering is made), 20 ℃ of measurements.
(7) water-fast crumbliness
To drop in the water of 150ml normal temperature on 50 on 150 ℃ of following exsiccant samples, and see to have or not broken sample, to judge its water tolerance.Break if any several samples, think that then this sample is not good,, then think good as not breaking fully.Embodiment 1
With median size is that the gibbsite type aluminium-hydroxide powder H-32 of electrician's system (clear and) of 8 μ m as solids (SP), is scattered in SiO
2In No. 3 sodium silicate solutions (A solution) of the 0.147g/ml concentration of meter, will be with the SiO that contains in this A solution
2Meter, SiO
2: SP=85: the sulfuric acid of 15 sodium silicate solution and 10% concentration is by 3mm diameter, the long second fluid nozzle of 200mm, respectively with the speed of 3.6 liters/mim and 1.5 liters/mim, from relief outlet slightly be inclined upwardly about 80 the degree, with two kinds of instantaneous mixing of fluid, discharge that (outlet pressure is about 3.5kg/cm in atmosphere
2).Then, make it fall to 20m
3In the water of stainless steel storagetank, at room temperature, wear out in the scope of pH8-10, by the sol gel reaction of silicon-dioxide, the preparation spherical silica-gel then, adds concentration and is 40% sulfuric acid, make its whole pH reach 3-4 after, be about 2.5m
3Washing under the current of/hr flow velocity, is 6000 Ω cm until the ratio resistance of washing lotion.Again 130-140 ℃ down dry, the median size of No.S-1 that obtains sample of the present invention is at the spherical silica-gel of 4.3mm.This spherical silica-gel median size is 4mm, and micropore volume-2 is 0.15cc/g, and tamped density is 0.600g/ml, and compressive strength is 18kgf, and water-fast crumbliness is good.Embodiment 2
Similarly to Example 1, difference is that the SiO 2 powder that with median size is 6 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.100g/ml concentration of meter (in the A solution, viscosity=8cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=95: the sulfuric acid of 5 sodium silicate solution and 6% concentration obtains the sample No.S-2 of spherical silica-gel of the present invention.This spherical silica-gel median size is 3mm, and micropore volume is 0.12cc/g, and tamped density is 0.650g/ml, and compressive strength is 17kgf, and water-fast crumbliness is good.Embodiment 3
Similarly to Example 1, difference is that the titanium dioxide powder that with median size is 0.7 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=85: the sulfuric acid of the sodium silicate solution of 15 weight ratios and 10% concentration obtains the sample No.S-3 of spherical silica-gel of the present invention.This spherical silica-gel median size is 5mm, and micropore volume is 0.13cc/g, and tamped density is 0.630g/ml, and compressive strength is 15kgf, and water-fast crumbliness is good.Embodiment 4
Similarly to Example 1, difference is that the Zirconium oxide powder that with median size is 1 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=80: the sulfuric acid of the sodium silicate solution of 20 weight ratios and 10% concentration obtains the sample No.S-3 of spherical silica-gel of the present invention.This spherical silica-gel median size is 5.3mm, and micropore volume-2 is 0.14cc/g, and tamped density is 0.640g/ml, and compressive strength is 16kgf, and water-fast crumbliness is good.Embodiment 5
Similarly to Example 1, difference is that the active carbon powder that with median size is 2 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=97: the sulfuric acid of the sodium silicate solution of 3 weight ratios and 10% concentration obtains the sample No.S-5 of spherical silica-gel of the present invention.This spherical silica-gel median size is 4.8mm, and micropore volume is 0.1cc/g, and tamped density is 0.650g/ml, and compressive strength is 15kgf, and water-fast crumbliness is good.Embodiment 6
Similarly to Example 1, difference is that the vanadium oxide powder that with median size is 6 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=85: the sulfuric acid of the sodium silicate solution of 15 weight ratios and 10% concentration obtains the sample No.S-6 of spherical silica-gel of the present invention.This spherical silica-gel median size is 5mm, and micropore volume-2 is 0.08cc/g, and tamped density is 0.660g/ml, and compressive strength is 16kgf, and water-fast crumbliness is good.Embodiment 7
Similarly to Example 1, difference is that the niobium oxide powder that with median size is 4 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=90: the sulfuric acid of the sodium silicate solution of 10 weight ratios and 10% concentration obtains the sample No.S-7 of spherical silica-gel of the present invention.This spherical silica-gel median size is 6mm, and micropore volume-2 is 0.13cc/g, and tamped density is 0.690g/ml, and compressive strength is 17kgf, and water-fast crumbliness is good.Embodiment 8
Similarly to Example 1, difference is that the chromium oxide powder that with median size is 6 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=90: the sulfuric acid of the sodium silicate solution of 10 weight ratios and 10% concentration obtains the sample No.S-8 of spherical silica-gel of the present invention.This spherical silica-gel median size is 4.6mm, and micropore volume-2 is 0.10cc/g, and tamped density is 0.690g/ml, and compressive strength is 18kgf, and water-fast crumbliness is good.Embodiment 9
Similarly to Example 1, difference is that the molybdenum oxide powder that with median size is 5 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.150g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=60: the sulfuric acid of the sodium silicate solution of 40 weight ratios and 10% concentration obtains the sample No.S-9 of spherical silica-gel of the present invention.This spherical silica-gel median size is 5mm, and micropore volume-2 is 0.14cc/g, and tamped density is 0.670g/ml, and compressive strength is 17kgf, and water-fast crumbliness is good.Embodiment 10
Similarly to Example 1, difference is that the Tungsten oxide 99.999 powder that with median size is 5 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=85: the sulfuric acid of the sodium silicate solution of 15 weight ratios and 10% concentration obtains the sample No.S-10 of spherical silica-gel of the present invention.This spherical silica-gel median size is 5mm, and micropore volume-2 is 0.12cc/g, and tamped density is 0.700g/ml, and compressive strength is 16kgf, and water-fast crumbliness is good.Embodiment 11
Similarly to Example 1, difference is that the manganese oxide powder that with median size is 3 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=85: the sulfuric acid of the sodium silicate solution of 15 weight ratios and 10% concentration obtains the sample No.S-11 of spherical silica-gel of the present invention.This spherical silica-gel median size is 5mm, and micropore volume-2 is 0.13cc/g, and tamped density is 0.680g/ml, and compressive strength is 15kgf, and water-fast crumbliness is good.Embodiment 12
Similarly to Example 1, difference is that the croci that with median size is 0.5 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=90: the sulfuric acid of the sodium silicate solution of 10 weight ratios and 10% concentration obtains the sample No.S-12 of spherical silica-gel of the present invention.This spherical silica-gel median size is 4.8mm, and micropore volume-2 is 0.11cc/g, and tamped density is 0.670g/ml, and compressive strength is 17kgf, and water-fast crumbliness is good.Embodiment 13
Similarly to Example 1, difference is that the cobalt oxide powder that with median size is 010 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=95: the sulfuric acid of the sodium silicate solution of 5 weight ratios and 10% concentration obtains the sample No.S-13 of spherical silica-gel of the present invention.This spherical silica-gel median size is 4.3mm, and micropore volume-2 is 0.13cc/g, and tamped density is 0.650g/ml, and compressive strength is 18kgf, and water-fast crumbliness is good.Embodiment 14
Similarly to Example 1, difference is that the nickel oxide powder that with median size is 2 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=95: the sulfuric acid of the sodium silicate solution of 5 weight ratios and 10% concentration obtains the sample No.S-14 of spherical silica-gel of the present invention.This spherical silica-gel median size is 5mm, and micropore volume-2 is 0.13cc/g, and tamped density is 0.670g/ml, and compressive strength is 17kgf, and water-fast crumbliness is good.Embodiment 15
Similarly to Example 1, difference is that the zeolite powder that with median size is 3 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=55: the sulfuric acid of the sodium silicate solution of 45 weight ratios and 10% concentration obtains the sample No.S-15 of spherical silica-gel of the present invention.This spherical silica-gel median size is 5.5mm, and micropore volume-2 is 0.14cc/g, and tamped density is 0.680g/ml, and compressive strength is 15kgf, and water-fast crumbliness is good.Embodiment 16
Similarly to Example 1, difference is that the wilkinite powder that with median size is 13 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=90: the sulfuric acid of the sodium silicate solution of 10 weight ratios and 10% concentration obtains the sample No.S-16 of spherical silica-gel of the present invention.This spherical silica-gel median size is 4.8mm, and micropore volume-2 is 0.12cc/g, and tamped density is 0.650g/ml, and compressive strength is 15kgf, and water-fast crumbliness is good.Embodiment 17
Similarly to Example 1, difference is that the acidic white earth powder that with median size is 15 μ m is scattered in SiO as solids (SP)
2Commercially available No. 3 sodium silicate solutions of the 0.225g/ml concentration of meter (in the A solution, viscosity=12cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=80: the sulfuric acid of the sodium silicate solution of 20 weight ratios and 12% concentration obtains the sample No.S-17 of spherical silica-gel of the present invention.This spherical silica-gel median size is 5mm, and micropore volume-2 is 0.13cc/g, and tamped density is 0.690g/ml, and compressive strength is 15kgf, and water-fast crumbliness is good.Embodiment 18
Similarly to Example 1, difference is, is solids (SP) outside the rich magnesium montmorillonite powder of synthetic laminated clay compound of 10 μ m with median size, is scattered in SiO
2Commercially available No. 3 sodium silicate solutions of the 0.147g/ml concentration of meter (in the A solution, viscosity=10cp), use the SiO to contain in this A solution
2Meter, SiO
2: SP=90: the sulfuric acid of the sodium silicate solution of 5 weight ratios and 10% concentration obtains the sample No.S-18 of spherical silica-gel of the present invention.This spherical silica-gel median size is 5.2mm, and micropore volume-2 is 0.11cc/g, and tamped density is 0.670g/ml, and compressive strength is 16kgf, and water-fast crumbliness is good.Embodiment 19
Similarly to Example 1, difference is that water glass and vitriolic mixed solution are emitted downwards, obtains the sample No.-19 of spherical silica-gel of the present invention.This spherical silica-gel median size is 400 μ m, and micropore volume-2 is 0.14cc/g, and tamped density is 0.680g/ml, and compressive strength is 19kgf, and water-fast crumbliness is good.Comparative example 1
Will be with SiO
2Count commercially available No. 3 sodium silicate solutions of 0.147g/ml concentration and the sulfuric acid of 10% concentration, by 3mm diameter, the long second fluid nozzle of 200mm, respectively with the speed of 3.6 liters/mim and 1.5 liters/mim, from relief outlet slightly be inclined upwardly about 80 the degree, two kinds of fluids are done instantaneous mixing, discharge that (outlet pressure is about 3.5kg/cm in atmosphere
2).Then, make it fall to 20m
3The water of stainless steel storagetank in, at room temperature, wear out in the scope of pH8-10, by the sol gel reaction of silicon-dioxide, the preparation spherical silica-gel then, adds concentration and is 40% sulfuric acid, make its whole pH reach 3-4 after, be about 2.5m
3Washing under the current of/hr flow velocity, is 6000 Ω cm until the ratio resistance of washing lotion.Dry under 130-140 ℃ again, obtain spherical silica-gel.This spherical silica-gel median size is 4.2 μ m, micropore volume 0.05cc/g, and tamped density is 0.730g/ml, water-fast broken number is 70%.The invention effect
According to the present invention, can obtain macropore and enlarge markedly, water-fast crushing performance is also improved significantly, and its endurance quality for temperature variation, pressure change improves the spherical silica-gel that the speed when absorption, desorb also obviously improves.Simultaneously, the method that is used for solids being scattered in alkali silicate or first machine acid of its necessity also has such advantage: manufacture method is easy, can make spherical silica-gel efficiently with less operation.The simple declaration of accompanying drawing
Among Fig. 1, just by the alkali silicate solution that has wherein disperseed aluminium hydroxide and inorganic acid reaction and the spherical silica-gel that obtains, and the spherical silica-gel that just obtains by the alkali silicate of fusion aluminium hydroxide not and inorganic acid reaction, done pictorialization by the relation of the pore radius of mercury penetration method gained and micropore volume.
Among Fig. 2, just by the mineral acid that has wherein disperseed the amorphous silica powder and alkali silicate solution reaction and the spherical silica-gel that obtains, and the spherical silica-gel that just obtains by the mineral acid of fusion amorphous silica powder not and alkali silicate solution reaction, done pictorialization by the pore radius of mercury penetration method gained and micropore volume relation.
Claims (11)
1. the manufacture method of a spherical silica-gel, this method system does instantaneous mixing with alkali silicate solution and mineral acid, make it form colloidal sol, again the colloidal sol that forms is discharged in gas-solvent, form colloid, form spherical silica-gel thus, it is characterized in that, in such manufacture method, the water-insoluble solid particle is scattered among at least a solution in alkali silicate solution or the first machine acid as macropore promotor.
2. manufacture method as claimed in claim 1, it is characterized in that described solids are oxide compound, composite oxides, oxyhydroxide or the complex hydroxide of the element of periodic table of elements group III A, IVA family, IVB family, VB family or group VIII.
3. manufacture method as claimed in claim 2 is characterized in that, described solids are aluminum oxide, silicon-dioxide, titanium oxide or zirconium white.
4. manufacture method as claimed in claim 1 is characterized in that, described solids are frame shape aluminosilicate or layer aluminosilicate, their acid treatment thing or baked article.
5. as claim 1 or 4 described manufacture method, it is characterized in that described solids are natural or synthetic clay or zeolite.
6. manufacture method as claimed in claim 1 is characterized in that, described solids are gac.
7. as each described manufacture method of claim 1 to 6, it is characterized in that described solids are the particle of median size 0.1-15 μ m.
8. as each described manufacture method of claim 1 to 7, it is characterized in that described solids are with the silicon-dioxide (SiO in the alkali silicate
2) be the benchmark meter, SiO
2And solids (SP) are with 95: 5-55: 45 weight ratio is used.
9. as each described manufacture method of claim 1 to 7, it is characterized in that the viscosity that is dispersed with the alkali silicate solution of solids or mineral acid is below 20 centipoises.
10. as each described manufacture method of claim 1 to 9, it is characterized in that the concentration of alkali silicate solution is with silicon-dioxide (SiO
2) be the benchmark meter, be 100-225g/l.
11. a spherical silica-gel is characterized in that, described spherical silica-gel is made up of the matrix of silica gel and the water-insoluble solid particle as macropore promotor that is scattered in this silica matrix; SiO in this matrix
2And solids (SP) are with 95: 5-55: 45 weight ratio exists; And have with mercury penetration method micropore volume measured, 0.08ml/g and water-fast crumbliness in the scope of the pore radius of 7.5-7500nm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP275441/95 | 1995-10-24 | ||
| JP27544195A JP3487987B2 (en) | 1995-10-24 | 1995-10-24 | Spherical silica gel with increased macropores and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1157260A true CN1157260A (en) | 1997-08-20 |
| CN1090589C CN1090589C (en) | 2002-09-11 |
Family
ID=17555575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96122871A Expired - Lifetime CN1090589C (en) | 1995-10-24 | 1996-10-23 | Macropore amplifying spherical silica-gel and its manufacturing method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3487987B2 (en) |
| CN (1) | CN1090589C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436316C (en) * | 2005-12-16 | 2008-11-26 | 厦门大学 | Preparation method of silica gel carrier |
| CN105195087A (en) * | 2015-10-26 | 2015-12-30 | 王立卓 | Extra-large-aperture silicon dioxide new material and preparation method thereof |
| CN105985458A (en) * | 2015-02-02 | 2016-10-05 | 中国石油天然气股份有限公司 | Silica gel/clay composite carrier, chromium catalyst, preparation method and application thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4784719B2 (en) * | 2001-04-02 | 2011-10-05 | 直弘 曽我 | Method for producing inorganic porous composite containing dispersed particles |
| JP2004224816A (en) * | 2003-01-20 | 2004-08-12 | Emulsion Technology Co Ltd | Aqueous non-slip coating material composition |
| JP4693531B2 (en) * | 2005-07-13 | 2011-06-01 | 株式会社トクヤマ | Method for producing dual pore silica |
| JP5646143B2 (en) * | 2008-12-26 | 2014-12-24 | 日揮触媒化成株式会社 | Flaky composite silica fine particle dispersion and method for producing the same |
| JP7079057B2 (en) * | 2018-09-28 | 2022-06-01 | 太平洋セメント株式会社 | Silica cleaning method |
| JP7174483B2 (en) * | 2018-10-17 | 2022-11-17 | 太平洋セメント株式会社 | Silica purification method and silica particles |
| CN115448316B (en) * | 2022-09-21 | 2024-02-27 | 江西联锴化学有限公司 | Preparation method of large-aperture spherical silicon dioxide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5084516A (en) * | 1973-11-30 | 1975-07-08 | ||
| JPS5085608A (en) * | 1973-11-30 | 1975-07-10 | ||
| CN1005404B (en) * | 1987-03-02 | 1989-10-11 | 中国石油化工总公司上海石油化工研究所 | Method for preparing silica gel with adjustable pore structure and without cracking when meeting water |
-
1995
- 1995-10-24 JP JP27544195A patent/JP3487987B2/en not_active Expired - Lifetime
-
1996
- 1996-10-23 CN CN96122871A patent/CN1090589C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436316C (en) * | 2005-12-16 | 2008-11-26 | 厦门大学 | Preparation method of silica gel carrier |
| CN105985458A (en) * | 2015-02-02 | 2016-10-05 | 中国石油天然气股份有限公司 | Silica gel/clay composite carrier, chromium catalyst, preparation method and application thereof |
| CN105985458B (en) * | 2015-02-02 | 2018-12-25 | 中国石油天然气股份有限公司 | Silica gel/clay composite carrier, chromium catalyst, preparation method and application thereof |
| CN105195087A (en) * | 2015-10-26 | 2015-12-30 | 王立卓 | Extra-large-aperture silicon dioxide new material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09110413A (en) | 1997-04-28 |
| CN1090589C (en) | 2002-09-11 |
| JP3487987B2 (en) | 2004-01-19 |
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