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CN104803390A - Silica gel and manufacturing method thereof, silica gel loaded paper and silica gel element - Google Patents

Silica gel and manufacturing method thereof, silica gel loaded paper and silica gel element Download PDF

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Publication number
CN104803390A
CN104803390A CN201510124584.8A CN201510124584A CN104803390A CN 104803390 A CN104803390 A CN 104803390A CN 201510124584 A CN201510124584 A CN 201510124584A CN 104803390 A CN104803390 A CN 104803390A
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silica gel
pore
pore diameter
paper
hydrogel
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米田雅彦
松村裕司
山名和树
浅野昭
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Nichias Corp
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Nichias Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Drying Of Gases (AREA)
  • Silicon Compounds (AREA)

Abstract

提供吸湿量在低湿度及高湿度下均都显著地高的硅胶、硅胶负载纸张以及硅胶元件，而且提供易于合成的硅胶的制造方法。在细孔直径为2.5nm以下的区域存在细孔分布的峰值(最大值)，而且细孔直径为10～25nm的总细孔容积(V1)和细孔直径为2～25nm的总细孔容积(V2)之比(V1/V2)为0.15～0.4的硅胶、其制造方法、负载该硅胶而成的硅胶负载纸张以及硅胶元件。

To provide silica gels, silica gel-loaded papers, and silica gel elements having significantly high moisture absorption at both low and high humidity levels, and to provide methods for the manufacture of easily synthesized silica gels. The peak (maximum value) of the pore distribution exists in the region with a pore diameter of 2.5 nm or less, and the total pore volume (V 1 ) with a pore diameter of 10 to 25 nm and the total pores with a pore diameter of 2 to 25 nm Silica gel having a volume (V 2 ) ratio (V 1 /V 2 ) of 0.15 to 0.4, a production method thereof, a silica gel-loaded paper and a silica gel element loaded with the silica gel.

Description

Silica gel and manufacture method, silica gel loaded paper and silica gel component
The divisional application of the patent application of " silica gel and manufacture method, silica gel loaded paper and silica gel component " that the application is application number is 200910002057.4, the applying date, to be January 12, denomination of invention in 2009 be.
Technical field
The present invention relates to the silica gel and manufacture method, silica gel loaded paper and silica gel component with the especially superior novel pore structure (pore structure) of wet-out property.
Background technology
From in the past, widely used silica gel, zeolite (zeolite) the even load honeycomb structured body of moisture adsorbent (honeycomb structural body) as dehumidification element.If silica gel and zeolite facies are compared, then the moisture uptake of zeolite is many at low relative humidity usually, and the moisture absorption quantitative change of silica gel is many when relative humidity is high.In addition, even if be all silica gel, but the moisture uptake of A type silica gel is relatively many at low relative humidity, and its moisture uptake uprises along with relative humidity and culminates; The moisture uptake of Type B silica gel is probably very low when relative humidity is less than 90%, and shows very high moisture uptake when the relative humidity of relative humidity more than 90% is high.
In JIS Z0701 (packaging silica-gel drier), A type is defined as " type that moisture adsorption power is under the low humidity strong ", Type B is defined as " adsorbing a large amount of moistures at high humidity; the type that loading capacity is large ", and define the rate of moisture absorption of A type under relative humidity 20%, 50% and 90% and be respectively " more than 8.0, more than 20.0, more than 30.0 ", the rate of moisture absorption of Type B under relative humidity 20%, 50% and 90% is respectively " more than 3.0, more than 10.0, more than 50.0 ".
On the other hand, TOHKEMY 2001-9231 publication discloses a kind of dehumidizier, this dehumidizier refers to, for silicon oxide 90.0 ~ 99.9 mass parts as silica gel, has coordinated the dehumidizier of mixture 0.1 ~ 10.0 mass parts of ferric oxide or ferric oxide and other metal oxides.This dehumidizier by the impact of humidity environment, does not have high hygroscopic property.
Patent documentation 1:JP JP 2001-9231 publication (claim 1)
But there are the following problems: the rate of moisture absorption of A type silica gel is little at high humidity; The rate of moisture absorption of Type B silica gel is little under the low humidity.Therefore, present situation is exactly, and when A type silica gel or Type B silica gel are used as dehumidizier, distinguish use these dehumidiziers according to humidity environment.In addition, although the moisture adsorbent described in TOHKEMY 2001-9231 publication has excellent hygroscopic property as above, still also exist as the low problem of the moisture uptake at high humidity of the intrinsic feature of silica gel.
Therefore, if all high silica gel of moisture uptake under low humidity and high humidity can be obtained, then can reuse under low humidity conditions and under high humidity, so exceedingly useful element can be provided.In addition, silica gel synthesis easier than zeolite and regeneration temperature is low, can reduce the plurality of advantages such as manufacturing cost and maintenance cost so have simultaneously.
Summary of the invention
Therefore, the object of the invention is to, be provided in silica gel, silica gel loaded paper and silica gel component that moisture uptake under low humidity and high humidity is high all significantly, and provide synthesis to be easy to the manufacture method of silica gel.
Under these circumstances, the result that the present inventor etc. study intensively, work out following content etc., the present invention is completed with this, foregoing is: if adopt and that the obtain droplet drying thing of semi-solid shape in addition dry to the drop of sodium silicate aqueous solution as the synthesis material of gelation object, then in gelation operation afterwards, generation gelation from the near surface of droplet drying thing, so can little pore be formed in skin section and form large pore at central part, its result, the silica gel of the Novel hole structure distributing different at the pore of skin section and central part can be obtained.
That is, the invention provides a kind of silica gel, it is characterized in that, there is the peak value (maximum value) of pore distribution in the region that pore diameter is below 2.5nm, and pore diameter is total pore volume V of 10 ~ 25nm 1with total pore volume V that pore diameter is 2 ~ 25mm 2ratio V 1/ V 2be 0.15 ~ 0.4, and the pore diameter of skin section is little and the pore diameter of central part is large.
In addition, the invention provides a kind of manufacture method of silica gel, it is characterized in that, comprising: I operation, drying is carried out to the drop of sodium silicate aqueous solution, obtain the droplet drying thing that water retention is the semi-solid shape of 70 ~ 120%; II operation, carries out gelation process to the droplet drying thing obtained in I operation; III operation, cleaning to remove in the silicone-hydrogel (silica hydrogel) that obtains in II operation the sodium that remains, thus the little and silica gel that the pore diameter of central part is large of the pore diameter obtaining skin section.
In addition, the invention provides a kind of silica gel loaded paper, it is characterized in that, on cellulosic paper, the above-mentioned silica gel of load forms.
In addition, the invention provides a kind of silica gel component, it is characterized in that, above-mentioned silica gel loaded paper is formed and forms.
Silica gel of the present invention is the silica gel or its crushed material that have little pore in skin section and have the Novel hole structure of large pore at central part, if working load has the silica gel loaded paper of this silica gel or silica gel component to be used as hygroscopic element, then owing to having large pore, so it is many and be easy to the characteristic of dehumidification under the low humidity to have adsorptive capacity at high humidity, and owing to having little pore, be easy under the low humidity adsorb and the characteristic of not easily dehumidification so have.Therefore, the moisture uptake under low humidity and high humidity is high all significantly, and can reuse under low humidity conditions and under high humidity.In addition, according to the manufacture method of silica gel of the present invention, then can by the silica gel of simple method synthesizing new pore structure.
Accompanying drawing explanation
Fig. 1 shows the figure of an example of the pore distribution curve of silica gel of the present invention.
Fig. 2 is the figure for illustration of the droplet drying thing formation method in I operation.
Fig. 3 is the schematic perspective view of the silica gel component with ripple (corrugate) shape honeycomb structure.
Fig. 4 is by the schematic cross sectional views of silica gel component along the face cutting parallel with opening portion.
Fig. 5 is the pore distribution curve of the silica gel obtained in the silica gel of the 3rd embodiment and manufacturing processed thereof.
Fig. 6 is the pore distribution curve of the first ~ tetra-embodiment and silica gel A ~ D.
Fig. 7 is the pore distribution curve of the first embodiment and silica gel E ~ G.
Embodiment
There is the peak value (maximum value) of pore distribution in silica gel of the present invention, total pore volume V of pore diameter 10 ~ 25nm in the region that pore diameter is below 2.5nm 1with total pore volume V of pore diameter 2 ~ 25nm 2ratio V 1/ V 2be 0.15 ~ 0.4, be preferably 0.15 ~ 0.35.Thus, silica gel of the present invention becomes moisture uptake under low relative humidity and high relative humidity silica gel high all significantly.If V 1/ V 2too small, then moisture uptake at high humidity tails off, and if V 1/ V 2excessive, then moisture uptake under the low humidity tails off.
Total pore volume V 1and V 2refer to, according to the aggregate-value of the pore volume utilizing the pore distributed computation result of known BJH method to obtain.The full pore volume of total now, the pore in the scope of having carried out pore distributed computation becomes its object.In addition, the mensuration of pore adopts nitrogen adsorption isotherm measuring method, and resolving based on pore shape is columnar hypothesis.In addition, the pore of pore diameter less than 2nm cannot be measured, and pore diameter to exceed the pore of 50nm so few that can both to ignore.In addition, according to pore distribution curve, V can be obtained by hand computation or automatic calculating 1and V 2.In addition, the pore distribution comprising the silica gel of the pilot process silica gel obtained in building-up process in this manual refers to, all use BEL JAPAN, INC. BELSORP-mini II processed, by the distribution that BJH method is obtained, wherein, above-mentioned BJH method within degassed 3 hours, carries out pretreated method by heating under vacuum at 150 DEG C.
With reference to Fig. 1, an example of the pore distribution curve of silica gel of the present invention is described.Be have unimodal (monomodal) by the silica gel shown by the distribution of the pore of Fig. 1, be the region of below 2.5nm in pore diameter, there is the peak value P (maximum value) of pore distribution in Fig. 1 at 2.0nm place.That is, the distribution range of this silica gel is very wide, is distributed with the little pore that a lot of pore diameter is about 2nm, and there is the large pore that pore diameter is more than 10nm.There is the peak value of pore distribution in the region that Type B silica gel is such as 4.0 ~ 8.0nm in pore diameter.In addition, there is the peak value (maximum value) of pore distribution in the A type silica gel obtained by existing synthetic method, but on this pore distribution curve, substantially there is not the pore that pore diameter is 10 ~ 25nm in the region that pore diameter is below 2.5nm.
In addition, the pore distribution of silica gel of the present invention in skin section is different with the pore distribution at central part.That is, relatively little in the pore diameter of skin section, large in the pore diameter of central part.Central part and skin section do not form clear and definite layer, but the pore distribution with little pore is changed to the pore distribution with large pore continuously from the surface of silica gel particle towards center.
Other silica gel of the present invention is pulverized above-mentioned pore silica gel pockety and obtained.Shredding unit and pulverization conditions can adopt known method.Pulverizing the silica gel obtained is have the material pulverizing front silica gel structure and the mixture without the material pulverizing front silica gel structure, has the V of afore mentioned rules 1/ V 2ratio.
Silica gel of the present invention also can be the silica gel doped with transition metal or base metal (base metal).Thereby, it is possible to obtain the material of moisture absorption and desorption property excellence.That is, the preferred silica gel of the present invention has coordinated the oxide compound of transition metal or base metal to obtain in as the silicon oxide of silica gel.In silicon oxide 100 mass parts, the use level of the oxide compound of transition metal or base metal the chances are 0.1 ~ 10.0 mass parts.Transition metal and base metal can adopt iron, titanium, aluminium, zirconium, wherein, if excellent from the viewpoint of moisture absorption and desorption property, and preferably iron.
Silica gel of the present invention belongs to the A type silica gel of JIS Z0701 (packaging silica-gel drier), rate of moisture absorption under the relative humidity 20%, 50% and 90% that JIS specifies is respectively more than 8.0, more than 20.0, more than 30.0, and rate of moisture absorption under 90% is high, be more than 40.In addition, there is the peak value of pore distribution in silica gel of the present invention the region being such as 4.0 ~ 8.0nm in pore diameter unlike Type B silica gel.
Next, the manufacture method of silica gel of the present invention is described.The manufacture method of silica gel of the present invention has following I ~ III operation.
I operation is the operation obtaining droplet drying thing, in this I operation, in addition dry to make its water retention be preferably 50 ~ 150%, to be particularly preferably 70 ~ 120% to the drop of sodium silicate aqueous solution, obtains the droplet drying thing of semi-solid shape thus.In addition, water retention 100% means the quality of water glass and the identical in quality of water.Diminish on the whole if water retention crosses pore diameter at least, thus specific surface area diminishes, this is unfavorable for the present invention, and if water retention is too much, then dissolved when carrying out gelation, so be difficult to form large pore, this is unfavorable for the present invention.About sodium silicate aqueous solution, the sodium silicate aqueous solution used when synthesizing existing silica gel can be adopted equally.
Sodium silicate aqueous solution drips on the hydrophobicity thin slices such as fluoro-resin sheet (fluororesin sheet) and obtained by droplet drying thing.Such as, in this point that can obtain a large amount of silica gel, on hydrophobicity thin slice 11, preferably form the method for the drop 21 of multiple sodium silicate aqueous solution as shown in Figure 2.Drying conditions to make the water retention of drop be in condition in above-mentioned scope, specifically, and in the drying machine of 70 ~ 110 DEG C dry 1 ~ 5 minute.If the water retention of droplet drying thing is in above-mentioned scope, the water retention that then can become relatively skin section low and the semisolid that the water retention of inside is high or the material close to solid, by carrying out gelation to it, the pore diameter that can obtain relatively skin section is little and at the large silica gel of the pore diameter of central part, can obtain the silica gel that moisture uptake is all excellent in two kinds of situations that relative humidity is high and low thus.
Such as according to the weight determination result of dry front and back, the amount of moisture in the droplet drying thing of semi-solid shape can be obtained.Its maximum length of droplet drying thing of semi-solid shape is about 0.5 ~ 10mm.If maximum length is too small, then cannot obtain desired pore distribution, this is unfavorable for the present invention, and if diameter is excessive, then cannot carry out gelation to its inside, this is unfavorable for the present invention.The maximum length of the droplet drying thing of semi-solid shape refers to, from maximum length during top view droplet drying thing (overlooking).
Semi-solid shape refers to the state without mobility, even if make hydrophobicity thin slice tilt also can not flow.In addition, because droplet drying thing is attached on hydrophobicity thin slice, as long as so be immersed in gelating soln by whole hydrophobicity thin slice, dipping method is also simple.Like this, not using the water glass raw material before gelation as in this point that solution uses, the present invention's tool compared with existing synthesis method makes a big difference.
II operation is the operation that the droplet drying thing obtained I operation carries out gelation.That is, in II operation, droplet drying thing is impregnated in aqueous acid, with this, de-sodium is carried out to water glass and obtain silicone-hydrogel (silica hydrogel).As aqueous acid, can illustrate aqueous sulfuric acid or aqueous hydrochloric acid, pH value is 0.5 ~ 1.8, is preferably 0.8 ~ 1.3.Can containing pH value adjusting agents such as ammonium sulfate in aqueous acid.
Preferred immersion condition when have employed Sulfuric Acid-Ammonia solution as aqueous acid is, when pH value 0.5 ~ 1.8, dipping temperature 20 ~ 45 DEG C, more than 15 minutes, especially when pH value 0.7 ~ 1.5, dipping temperature 25 ~ 43 DEG C, 15 ~ 50 minutes, and then, when pH value 0.8 ~ 1.3, dipping temperature 30 ~ 42 DEG C, 15 ~ 50 minutes.If be in above-mentioned scope, then the specific surface area of final obtained silica gel is 550m 2/ more than g, this is conducive to the present invention.
II operation by above-mentioned gelation process, the silicone-hydrogel that the large pore that can obtain more than 10nm exists in a large number.Forming such reason comprising the silicone-hydrogel of large pore may be exactly distinctive gelification, this distinctive gelification refers to, the aqueous acid of pH value 0.5 ~ 1.8 soaks into inside from the surface of the droplet drying thing of the high water glass of pH value, thus from surface de-sodium to carry out gelation.The pore distribution of the silicone-hydrogel that II operation obtains is that pore diameter is 2 ~ 50nm, V 1/ V 2be probably 0.3 ~ 0.5, average pore diameter is 5 ~ 9nm, specific surface area is 100 ~ 350m 2the pore that the scope of/g is very wide distributes.
III operation is the operation of the sodium that left behind in the silicone-hydrogel that obtains of cleaning removing II operation.2 operations of pickling and washing are preferably carried out in cleaning, reliably can remove the sodium composition that left behind in silicone-hydrogel, reliably can remove the sodium sulfate in silica gel and unnecessary acid in rear operation in front operation.The aqueous sulfuric acid of preferred employing pH value 0.7 ~ 0.8, carries out the pickling of about 10 minutes at the temperature of 15 ~ 25 DEG C.The pore distribution of the silicone-hydrogel that III operation obtains is that pore diameter is 2 ~ 50nm, V 1/ V 2value is probably 0.25 ~ 0.45, average pore diameter is 3.5 ~ 7nm, specific surface area is 200 ~ 450m 2the pore that the scope of/g is very wide distributes.The silicone-hydrogel that III operation obtains, its average pore diameter and V 1/ V 2the silicone-hydrogel that value all obtains than II operation is little, and its specific surface area becomes large.
In the manufacture method of silica gel of the present invention, IV operation and V operation can also be carried out.
IV operation is that clean silicon hydrogel III operation obtained is impregnated into containing the operation in the solution of transition metal salt or base-metal salt.By importing in silicone-hydrogel by transition metal or base metal, residual sodium composition can be removed, and form little pore while large pore can be made in silica gel to left behind.In addition, because residual sodium composition tails off, so the deterioration such as 105 DEG C × 100%, in 0.12MPa, the steam-treated of 48 hours can be suppressed.
As transition metal or base metal, the material same with the transition metal of above-mentioned silica gel or base metal of can illustrating.In addition, the transition metal salt of transition metal salt or base-metal salt preferably sulfuric acid or base-metal salt, particularly preferably ferric sulfate, Tai-Ace S 150.In addition, transition metal salt or base-metal salt also can adopt the combination of a kind or 2 kinds.
V operation is the operation that the transition metal that obtains IV operation or base metal doped silicon hydrogel (silicone-hydrogel doped with transition metal or base metal) are washed.By this operation, can remove and remain in unnecessary salt in transition metal or base metal doped silicon hydrogel and sodium.By known drying means, drying is carried out to the silicone-hydrogel after washing step, thus obtain silica gel of the present invention.
According to the manufacture method of silica gel of the present invention, then obtain silicone-hydrogel by being immersed in the low acid solution of pH value by the droplet drying thing of water glass high for pH value, so large pore can be formed in silicone-hydrogel inside.And, internally there is silicone-hydrogel containing transition metal or the base metal of large pore, so when keeping the inner large pore had, little pore can be formed at surface element.Therefore, the silica gel obtained by the method or its crushed material have the pore structure of non-existent uniqueness in the past, so the moisture uptake under low humidity and high humidity is high all significantly.
Silica gel loaded paper of the present invention load silica gel powder on cellulosic paper formed.The silica gel powder that silica gel loaded paper of the present invention uses is except being ground into preferred particle diameter, identical with the silica gel of the invention described above, therefore the description thereof will be omitted.
In silica gel loaded paper of the present invention, the average particulate diameter of silica gel powder is 1.0 ~ 10 μm, is preferably 2 ~ 8 μm.If the average particulate diameter of this silica gel powder is too small, then the size of this silica gel powder this Inter-fiber voids relative too diminishes, so this silica gel powder is easy to penetrate this Inter-fiber voids, thus this silica gel powder easily comes off from this cellulosic paper, in addition, if the average particulate diameter of this silica gel powder is excessive, then because this silica gel powder is excessive, so by silica gel paper powder load on paper time easily uneven, thus uniform load cannot be realized.
This cellulosic paper utilizes paper fiber to weaving cotton cloth or non-woven fabrics of carrying out that copy paper or duse process (dry forming) obtain.
As long as the fiber be used on this cellulosic paper is used in fiber in dehumidification element usually, then just there is no particular limitation, such as, can illustrate: the inorganic fibres such as silicon-aluminum fiber, silica fibre, sapphire whisker, mullite fiber, glass fibre, fibrous magnesium silicate, carbon fiber; The organic fibres such as polyethylene fibre, polypropylene fibre, nylon fiber, trevira, polyvinyl alcohol fiber, aramid fiber (aramid fiber), paper pulp fiber (pulp fiber), rayon fiber (rayon fiber).In addition, these fibers can adopt separately a kind, or also can adopt combination of more than two kinds.
The fiber diameter of the fiber on this cellulosic paper is not particularly limited, but be preferably 0.1 ~ 25 μm, be particularly preferably 0.5 ~ 10 μm, and the average fiber length of fiber on this cellulosic paper is preferably 0.1 ~ 50mm, is particularly preferably 10 ~ 20mm.By making this fiber diameter and this average fiber length be positioned at this scope, the physical strength of this cellulosic paper can be made to improve.
For to be weaved cotton cloth by this fibroplastic this or the Inter-fiber voids rate of this non-woven fabrics is not particularly limited, but be preferably 50 ~ 95%, be particularly preferably 70 ~ 95%.This Inter-fiber voids rate refers to, from this weave cotton cloth or the apparent volume (apparent volume) of this non-woven fabrics deduct this weave cotton cloth or this non-woven fabrics fiber volume part (below, also be designated as Inter-fiber voids), this weave cotton cloth or this non-woven fabrics apparent volume in shared ratio.By making this Inter-fiber voids rate be within the scope of this, this silica gel powder can be made not only to be carried on the outer surface of cellulosic paper but also to be carried in Inter-fiber voids, so the load quantitative change of this silica gel powder is many.In addition, this to be weaved cotton cloth or the thickness of this non-woven fabrics is not particularly limited, but be preferably 0.05 ~ 0.5mm, be particularly preferably 0.1 ~ 0.3mm.Be within the scope of this by making this thickness, the physical strength of this cellulosic paper can not only be made to increase, and can control as pressure-losses during silica gel component very low, also have, the charge capacity being carried on this silica gel powder in the Inter-fiber voids of this cellulosic paper also becomes many.
As the method be carried on by silica gel powder on cellulosic paper, can method be exemplified below: silica gel powder is copied together with inorganic fibre or organic fibre into method; Silica gel powder is coated in the method on cellulosic paper; At formed machining after cellulosic paper, be immersed in the method etc. in the slurry containing silica gel powder.Silica gel powder is copied together with inorganic fibre or organic fibre into method refer to, the slurry of preparation containing silica gel powder, more than the a kind fiber be selected from inorganic fibre and organic fibre, utilize this slurry copy paper and drying, obtain the method for silica gel loaded paper with this.As required, inorganic particle, inorganic Tackifier materials, condensing agent and condensation subsidy material etc. can also suitably be mixed to slurry.Inorganic particle such as can be illustrated the particle of aluminum oxide, mullite, silicon-dioxide and zirconium white etc.The average particulate diameter of inorganic particle is generally 0.5 ~ 60 μm, is preferably 3 ~ 15 μm.If average particulate diameter is within the scope of this, then plasticity is good, and this is conducive to the present invention.Condensing agent such as can be illustrated cationic starch.In addition, condensation subsidy material such as can be illustrated Tai-Ace S 150, aluminium hydroxide, carclazyte, alumina sol, colloid silica etc.As inorganic particle, inorganic Tackifier materials, condensing agent and condensation subsidy material, a kind in above-mentioned substance can be adopted, or the combination of two or more material in above-mentioned substance can be adopted.
By above-mentioned molding raw material blending dispersion is modulated slurry in water.Order by merging for raw material each in molding raw material is not particularly limited, as long as suitably carry out.Blending means can adopt known method, the method using blade mixer, kneading pulper etc. to come mixing water and raw material of such as can illustrating.
If suppose, the total amount of the molding raw material in slurry is 100 quality %, then the use level of inorganic fibre in the slurry or organic fibre is generally 30 ~ 70 quality %.If the use level of inorganic fibre or organic fibre is within the scope of this, then can obtain low-density structure, this is conducive to the present invention.
Suppose that the total amount of molding raw material is in the slurry 100 quality %, then the use level of silica gel powder is in the slurry generally 10 ~ 80 quality %, is preferably 30 ~ 70 quality %.If the use level of silica gel powder is in above-mentioned scope, even if then low density also obtains high strength, this is conducive to the present invention.
Slurry concentration i.e. molding raw material total content is in the slurry generally 0.1 ~ 10 quality %, is preferably 0.5 ~ 5 quality %.If slurry concentration is within the scope of this, then plasticity is good, and this is conducive to the present invention.
As method silica gel powder is coated on cellulosic paper, the method for slurry coating on cellulosic paper will be mixed to get for principal constituent with silica gel powder, organic binder bond and mineral binder bond of can illustrating.
Binding agent is for being fixed on cellulosic paper by silica gel powder.As this organic binder bond suitable have the organic binder bond such as acrylic adhesive, PVA class binding agent.Its reason is, the cellulosic paper after utilizing binding agent to fix can be made to have flexibility, prevent coming off of silica gel powder, and ripple processing (waveform processing) being used in shaping honeycomb structured body thus becomes possibility.
The organic binder bond addition of relative slurry total mass is preferably 1 ~ 20% when calculating with nonvolatile component, does not have effect on moisture extraction and does not need its attachment function after honeycomb shaping, so only use the minimum enough can fixing silica gel powder due to organic binder bond.
Silica gel component of the present invention forms above-mentioned silica gel powder loaded paper (below, also referred to as " loaded paper ") to obtain.Shape for silica gel component is not particularly limited, the corrugated honeycomb structure that the loaded paper such as can illustrating alternately laminated undulatory loaded paper and even shape obtains, to stack gradually the structure etc. that the loaded paper of pleated processed with corrugated and the loaded paper of even shape obtain at a right angle with ventilation direction, wherein, because the stream of the processed gas in corrugated honeycomb structure is parallel with ventilation direction, so the pressure-losses is low, in this, this corrugated honeycomb structure is preferred structure.
With reference to Fig. 3 and Fig. 4, this corrugated honeycomb structure is described.Fig. 3 is the schematic perspective view of the silica gel component 2 with this corrugated honeycomb structure.In silica gel component 2, be alternately laminated with this even shape loaded paper 3 and corrugated loaded paper 4.Between this even shape loaded paper 3 and this corrugated loaded paper 4, the continuous print direction, crest portion 5 be formed along this corrugated loaded paper 4 extend roughly half-terete empty 6.And processed gas can by cavity 6.
This even shape loaded paper 3 is weaved cotton cloth or the even shape thing of non-woven fabrics with fibroplastic by this paper, and this corrugated loaded paper 4 to be weaved cotton cloth to this or the even shape thing of this non-woven fabrics carries out ripple and shapes paper into waveform.The processing of this ripple refers to, makes this thing such as even shape such as even shape loaded paper 3 grade by between upper and lower a pair waveform stepped roll, is configured as the working method of waveform shape with this.
And even shape loaded paper 3 and corrugated loaded paper 4 are that core paper is alternately laminated with this corrugated loaded paper 4, form this silica gel component 2 with this.In the case, this even shape loaded paper 3 and this corrugated loaded paper 4 as core paper, can adopt and carry out shape all-in-one-piece structure by the upper and lower crest portion 5,5 of this corrugated loaded paper 4 (core paper) of the bonding such as binding agent and this even shape loaded paper 3, also can adopt and do not carry out boning and be these paper stacked and the paper after stacked put into the structure that framework fixed.As this binding agent for bond this even shape loaded paper 3 and corrugated loaded paper 4, silicon sol etc. of such as can illustrating.
Fig. 4 is by the schematic cross sectional views of this silica gel component 2 along the face cutting parallel with opening portion 7.In the diagram, this crest portion 5 of this corrugated loaded paper 4 is bonded together with even shape loaded paper 3.Crest height (the Reference numeral h in Fig. 4) for this silica gel component 2 is not particularly limited, but is preferably 0.5 ~ 10mm, is particularly preferably 0.6 ~ 5mm, is more preferably 0.7 ~ 2mm.In addition, the pitch of waves (the Reference numeral p in Fig. 4) for this silica gel component 2 is not particularly limited, but is preferably 1 ~ 20mm, is particularly preferably 1 ~ 5mm, is more preferably 1.5 ~ 4mm.Because this crest height and this pitch of waves are within the scope of this, so the balance that the moisture in processed gas removes between efficiency and the pressure-losses improves.
Be impregnated in after forming processing to cellulosic paper in the method in the slurry containing silica gel powder, method cellulosic paper being formed to processing is identical with the method forming processing to above-mentioned silica gel powder loaded paper.In addition, by slurry preparation for its solid component concentration becomes 20 ~ 40 % by weight, and the molding of impregnation of fibers matter paper is with load silica gel powder.Suppose that solid component concentration is in the slurry 100 weight parts, then the use level of silica gel powder is in the slurry generally 50 ~ 95 weight portions, is preferably 70 ~ 90 weight portions.If the use level of silica gel powder is less than above-mentioned scope, then the ratio of binding agent etc. is high, so the intensity of molding uprises, but because the absolute magnitude of silica gel powder is few, so its wet-out property step-down, and if the use level of silica gel powder more than above-mentioned scope, then the quantitative change of binding agent etc. is few, so there is the phenomenon such as to come off of silica gel powder, cannot be applicable in practical application.
The moisture uptake of this silica gel component of the present invention under low humidity and high humidity is high all significantly.Therefore, silica gel component of the present invention has excellent performance as rotary regenerative dehumidifier element.
Next, more specifically describe the present invention by embodiment, but this just illustrates, and can not be considered as limitation of the invention.
First embodiment
(synthesis of silica gel)
Utilize drip nozzle, by SiO 2/ Na 2water glass (No. 3, the JIS) aqueous solution of O (mol ratio)=3 drips 30 μ L on the thin slice of fluorine-type resin at every turn, which form multiple drop.Drop is with suitable gap-forming.Then, in the drying machine of 110 DEG C, maintain 2 minutes, thus obtain the droplet drying thing (I operation) that water retention is the semi-solid shape of 100%.
Droplet drying thing on the fluorine-type resin thin slice obtained in I operation is separated from fluorine-type resin thin slice, and in 10% Sulfuric Acid-Ammonia solution of pH value 1,35 DEG C, impregnated of 60 minutes (II operation).By II operation, the water glass (Gui Suan ソ ー ダ) of droplet drying thing is become silicone-hydrogel by de-sodium.
Next, by the silicone-hydrogel that obtains in II operation dip pickling 10 minutes in 2% sulphuric acid soln of 20 DEG C.Next, carried out washing (III operation) to the silicone-hydrogel of pickling further.Washing conditions is flooded 10 minutes in the water of 20 DEG C by silicone-hydrogel.
Then, by the clean silicon hydrogel obtained in III operation 35 DEG C, impregnated of 30 minutes (IV operation) in 10% ferrum sulfuricum oxydatum solutum of pH value 1.2.In addition, further obtained ferric sulfate process silicone-hydrogel is washed.Then, at 110 DEG C, carry out the drying treatment of 3 hours, obtain iron content silica gel of the present invention.The specific surface area of obtained silica gel, pore distribution and fuchsin(e)test are measured.The standard of the fuchsin(e)test institute foundation of silica gel is JIS Z0701.In table 1 and table 2, respectively illustrate its result, figure 6 illustrates pore distribution curve.From the pore distribution curve of Fig. 6, the silica gel obtained has following unique pore structure: be about in pore diameter the peak value (maximum value) that 2.0nm place exists pore distribution, comprises pore diameter probably for the little pore of 2nm and pore diameter are both of the large pore of more than 10nm.In addition, as known from Table 2, the silica gel of the first embodiment has following feature: under low humidity (such as RH20%), as A type silica gel, rate of moisture absorption is high, and under high humidity (such as RH90%) as Type B silica gel rate of moisture absorption high.
Second and the 3rd embodiment
Except employing is flooded the immersion condition (the second embodiment) of 90 minutes, flooded the immersion condition (the 3rd embodiment) of 30 minutes to be substituted in except the immersion condition flooding 60 minutes in the 10% Sulfuric Acid-Ammonia solution of 35 DEG C in II operation in the 10% Sulfuric Acid-Ammonia solution of 35 DEG C in the 10% Sulfuric Acid-Ammonia solution of 35 DEG C, synthesize iron content silica gel by the method same with the first embodiment, and carry out same evaluation.In table 1 and table 2, respectively illustrate its result, figure 6 illustrates pore distribution curve.Same with the first embodiment, from second and the 3rd pore distribution curve of embodiment, the silica gel obtained has following unique pore structure: be about in pore diameter the peak value (maximum value) that 2.0nm place exists pore distribution, containing pore diameter probably for the little pore of 2nm and pore diameter are both of the large pore of more than 10nm.In addition, in figure 6, second and the 3rd embodiment pore distribution curve and the pore distribution curve of the first embodiment extremely approximate, both almost overlap.
In addition, as known from Table 2, second and the 3rd the silica gel of embodiment there is following feature: under low humidity (such as RH20%), as A type silica gel, rate of moisture absorption is high, and under high humidity (such as RH90%) as Type B silica gel rate of moisture absorption high.
In addition, in the third embodiment, the specific surface area of the silica gel after II operation and pore distribution are measured.Its result, specific surface area is 136m 2/ g, average pore diameter are 8.4nm, V 1/ V 2be 0.46.In addition, figure 5 illustrates pore distribution curve.In addition, in Figure 5, for the ease of comparing the pore distribution curve of the silica gel that also show the 3rd embodiment.It is the very wide pore distribution of the scope of the large pore of more than 10nm containing pore diameter that silica gel after II operation has a large amount of.It can thus be appreciated that the large pore in silica gel of the present invention is the pore that the part of the large pore generated in the aqueous gelled process by II operation remains to final operation always.
4th embodiment
Except adopting 10% alum liquor to replace except 10% ferrum sulfuricum oxydatum solutum in IV operation, synthesized containing aluminum silica gel by the method same with the first embodiment, and carried out same evaluation.In table 1 and table 2, respectively illustrate its result, figure 6 illustrates pore distribution curve.Same with the first embodiment, from the pore distribution curve of the 4th embodiment, the silica gel obtained has following unique pore structure: be about in pore diameter the peak value (maximum value) that 2.0nm place exists pore distribution, containing pore diameter probably for the little pore of 2nm and pore diameter are both of the large pore of more than 10nm.In addition, in figure 6, the pore distribution curve of the 4th embodiment and the pore distribution curve of the first embodiment extremely approximate, both roughly overlap.In addition, as known from Table 2, the silica gel of the 4th embodiment has following feature: under low humidity (such as RH20%), as A type silica gel, rate of moisture absorption is high, and under high humidity (such as RH90%) as Type B silica gel rate of moisture absorption high.
5th embodiment
(manufacture of silica gel component)
Pulverize the silica gel obtained in a first embodiment, obtain the Powdered silica gel that average particulate diameter is 1 ~ 10 μm.This Powdered silica gel and acrylic adhesive is mixed to get slurry, this slurry coating carried out drying on inorganic fibre paper, has made silica gel loaded paper with this.In addition, silica gel load amount is adjusted to 80 % by weight of silica gel loaded paper.Then, the structure that ripple is processed to form Fig. 4 is carried out to silica gel loaded paper, and this structure is bondd, make the element of honeycomb structure with this.
According to JIS Z0701 standard, fuchsin(e)test is carried out to the silica gel component obtained in the 5th embodiment.Show its result in table 3.
First comparative example
By known method water glass (Gui Suan ソ ー ダ) solution and sulphuric acid soln being mixed make them react, synthesize iron content silica gel.That is, be uniformly mixed 12% aqueous sulfuric acid 95 parts and 10% ferrum sulfuricum oxydatum solutum 5 parts, and drip SiO to this mixing solutions 2/ Na 2the SiO of the water glass (No. JIS3) of O (mol ratio)=3 2the aqueous solution of concentration 10%, to be adjusted to pH value 1.7, obtains silicon sol with this.Then, at 60 DEG C, heat 4 hours to implement gelation process, thus obtain silicone-hydrogel.After being broken into fritter, utilizing 0.5% uncommon sulfuric acid to clean, and then wash, then add ammoniacal liquor and make it become pH value 5.3, and carried out the slaking of heating of 60 DEG C × 1 hour.Then, after washing, carry out the drying treatment of 110 DEG C × 12 hours, then, after washing, carry out the drying treatment of 110 DEG C × 12 hours, obtain silica gel A with this.Show the physicals of obtained silica gel A in Table 1, figure 6 illustrates pore distribution curve.From the pore distribution curve of Fig. 6, pore diameter is that the large pore of more than 10nm is almost 0.
Second comparative example
Except adopting the pH value cooking conditions of heating of 6.5,60 DEG C × 1 hour to replace except the pH value cooking conditions of heating of 5.3,60 DEG C × 1 hour, obtain silica gel B by the method same with the first comparative example.Show the physicals of obtained silica gel B in Table 1, figure 6 illustrates pore distribution curve.From the pore distribution curve of Fig. 6, pore diameter is that the large pore of more than 10nm is almost 0.
3rd comparative example
Except adopting the pH value cooking conditions of heating of 6.5,60 DEG C × 3 hours to replace except the pH value cooking conditions of heating of 5.3,60 DEG C × 1 hour, obtain silica gel C by the method same with the first comparative example.Show the physicals of obtained silica gel C in Table 1, figure 6 illustrates pore distribution curve.From the pore distribution curve of Fig. 6, pore diameter is that the large pore of more than 10nm is almost 0.
4th comparative example
Except adopting the pH value cooking conditions of heating of 9.8,60 DEG C × 1 hour to replace except the pH value cooking conditions of heating of 5.3,60 DEG C × 1 hour, obtain silica gel D by the method same with the first comparative example.Show the physicals of obtained silica gel D in Table 1, figure 6 illustrates pore distribution curve.From the pore distribution curve of Fig. 6, silica gel D is about in pore diameter the peak value (maximum value) that 6.0mm place exists pore distribution, and there is the large pore that pore diameter is more than 10mm, but be a kind ofly be 5.0% at relative humidity 20% time rate of moisture absorption, be 13.6% at relative humidity 50% time rate of moisture absorption, be the Type B silica gel of 60.4% at relative humidity 90% time rate of moisture absorption.Therefore, its adsorptive power under low humidity (such as RH20%) is weak.
Five ~ seven comparative examples
The pore distribution of 3 kinds of A type silica gel that market is sold and silica gel E ~ G is measured.In the figure 7, its result is together illustrated with the first embodiment.In addition, the physical properties of silica gel E ~ G is shown in Table 1.Its average pore diameter of any silica gel in silica gel E ~ G is 2.2 ~ 2.3nm, its V 1/ V 2value is 0.01 ~ 0.07.In addition, from pore distribution curve, be about in pore diameter the peak value (maximum value) that 2.0nm place exists pore distribution, and pore diameter is that the large pore of more than 10nm is almost 0.
8th comparative example and the 9th comparative example
Except adopting the silica gel E (the 9th comparative example) of the silica gel A of the first comparative example (the 8th comparative example) and the 5th comparative example with except the silica gel replacing the first embodiment respectively, the method same by the 5th embodiment manufactures silica gel component, and evaluates its water absorbability.Show its result in table 3.
Table 1
Table 2
Fig. 3
From the result of table 1 ~ table 3 and Fig. 5 ~ 7, the silica gel of the first ~ 4th embodiment has and has little pore in skin section and the Novel hole structure at central part with large pore, form the silica gel component that obtains according to there being the silica gel loaded paper of its crushed material to load as hygroscopic element, then relative humidity be 20% ~ 90% low humidity and high humidity under moisture uptake high all significantly.On the other hand, the A type silica gel of the first ~ three comparative example and the five ~ seven comparative example owing to there is the pore of more than 10nm hardly, so the moisture uptake under high relative humidity is low.The Type B silica gel of the 4th comparative example, owing to there is the pore that pore diameter is 4 ~ 8mm in a large number, so be that moisture uptake under the high humidity of 90% is high in relative humidity, but is that moisture uptake under the low humidity of 20% is low significantly in relative humidity.

Claims (7)

1. a silica gel, is characterized in that, there is peak value and the maximum value of pore distribution in the region that pore diameter is below 2.5nm, pore diameter is total pore volume V of 10 ~ 25nm 1with total pore volume V that pore diameter is 2 ~ 25nm 2ratio V 1/ V 2be 0.15 ~ 0.4, and the pore diameter of skin section is little and the pore diameter of central part is large.
2. silica gel as claimed in claim 1, is characterized in that, containing transition metal or base metal.
3. a manufacture method for silica gel, is characterized in that, comprising:
I operation, carries out drying to the drop of sodium silicate aqueous solution, obtains the droplet drying thing that water retention is the semi-solid shape of 70 ~ 120%;
II operation, carries out gelation process to the droplet drying thing obtained in I operation;
III operation, cleaning to remove in the silicone-hydrogel that obtains in II operation the sodium that remains;
Thus the little and silica gel that the pore diameter of central part is large of the pore diameter obtaining skin section.
4. the manufacture method of silica gel as claimed in claim 3, is characterized in that, comprising:
IV operation, is immersed in the solution containing transition metal salt or base-metal salt by cleaned silicone-hydrogel;
V operation, washes the transition metal obtained in IV operation or base metal doped silicon hydrogel.
5. the manufacture method of silica gel as claimed in claim 3, it is characterized in that, the maximum length of the droplet drying thing of the semi-solid shape obtained in I operation is 0.5 ~ 10mm.
6. a silica gel loaded paper, is characterized in that, the silica gel on cellulosic paper described in load claims 1 or 2 forms.
7. a silica gel component, is characterized in that, forms form silica gel loaded paper according to claim 6.
CN201510124584.8A 2008-03-28 2009-01-12 Silica gel and manufacturing method thereof, silica gel loaded paper and silica gel element Pending CN104803390A (en)

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