CN101400440A - Method for producing adsorbent-containing form and adsorbent-containing form - Google Patents
Method for producing adsorbent-containing form and adsorbent-containing form Download PDFInfo
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- CN101400440A CN101400440A CNA2007800086335A CN200780008633A CN101400440A CN 101400440 A CN101400440 A CN 101400440A CN A2007800086335 A CNA2007800086335 A CN A2007800086335A CN 200780008633 A CN200780008633 A CN 200780008633A CN 101400440 A CN101400440 A CN 101400440A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- 239000003463 adsorbent Substances 0.000 title claims abstract description 44
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 144
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 141
- 239000010457 zeolite Substances 0.000 claims abstract description 141
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 77
- -1 silane alkoxide Chemical class 0.000 claims abstract description 61
- 229910000077 silane Inorganic materials 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000005520 cutting process Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000009736 wetting Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- 239000002274 desiccant Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 235000011837 pasties Nutrition 0.000 claims description 9
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000000499 gel Substances 0.000 abstract description 40
- 239000011240 wet gel Substances 0.000 abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 14
- 238000001879 gelation Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229920001817 Agar Polymers 0.000 description 7
- 239000008272 agar Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- 238000005213 imbibition Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- 241001466460 Alveolata Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 210000002706 plastid Anatomy 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- AXKGUOXGBWHEGY-UHFFFAOYSA-N silane 3-trimethoxysilylpropan-1-amine Chemical compound [SiH4].CO[Si](CCCN)(OC)OC AXKGUOXGBWHEGY-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention is to provide a method for manufacturing adsorbent-containing compact wherein the adsorbent-containing compact has 70 weight% or more of high contents of zeolite in order to maintain its high hardness and adsorbability. The present invention is to provide a method for manufacturing adsorbent-containing compact which is an easy manufacturing method with high safety even though the respective dies are not used, and to provide an adsorbent-containing compact obtained from the method for manufacturing the same. The method for manufacturing adsorbent-containing compact according to the present invention is characterized in that : A method for manufacturing adsorbent-containing compact comprising the steps of: forming a silane alkoxide hydrolyzed solution containing silane alkoxide and hydrochloric acid; mixing hydrophobic zeolite in said silane alkoxide hydrolyzed solution; hardening the mixed wet gel containing zeolite in to a wet gel body having more than 0% to 10% or lower of deformation ratio; cutting said wet gel body; drying said cut wet gel body to form a dry gel body. The adsorbent-containing compact according to the present invention is characterized in that it is obtained from the method of manufacturing the same.
Description
Technical field
The present invention relates to contain the manufacture method of adsorbent formed body and contain the adsorbent formed body, specifically, relate to according to the sol-gal process that uses hydrophobic zeolite, do not use a model separately and the manufacture method that contains the adsorbent formed body that contains the high concentration zeolite that is shaped and contain the adsorbent formed body by what this manufacture method obtained.
Background technology
At present, in order to adsorb the gas componant that contains moisture, use zeolite, still, under high humidity environment, the trend of the moisture more than the gas componant is adsorbed in existence, in order to make formed body, with situation that inorganic bond mixes under, zeolite carries out adsorption moisture, has the big and dangerous problem of thermal discharge.
Disclose the manufacture method of adsorbent composition in the patent documentation 1, the mixed solution of metal alkoxide solution and synthetic zeolite is hydrolyzed, synthetic zeolite is dispersed in the porous glass, make it fully dry then.But synthetic zeolite content is the low content below 30 weight %.
Disclose the inanimate matter composite functional material in the patent documentation 2,, the inanimate matter plural gel burnt till with 500 ℃ form according to sol-gal process by the mixture that contains organic metal alkoxide solution and inanimate matter powder.But synthetic zeolite content is the low content at 15wt%.
Disclose the zeolite porous plastid in the patent documentation 3, the clay of zeolite and inorganic binder is mixed with the power of the such physical property of ball mill and make its dispersion, and it is being burnt till more than 250 ℃.
When the formed body of the state of making the absorption affinity that keeps zeolite powder, zeolite powder content is become more than the 70 weight %, and wish to keep hardness.But, because zeolite powder does not have assembly, thereby difficulty.In addition, making zeolite 90 weight % beads (for example) with reference to patent documentation 4, still, because be that binding agent carries out the mixing comminutor manufacturing of using with the clay based material, so, bead shape just.
Therefore, do not use large-scale device, and with dry environments such as sintering than present also low temperature, the manufacture method that the formed body of zeolite more than 70 weight % of high rigidity is made as the shape that meets purposes such as fine shape is desirable.
In addition, when using separately metal pattern that formed body is shaped,, be inevitable by going into mould, playing the shortcoming, damaged many of the formed products that modulo operation causes.
Patent documentation 1:(Japan) spy opens flat 5-293371 communique
Patent documentation 2:(Japan) spy opens flat 3-285843 communique
Patent documentation 3:(Japan) spy opens clear 62-297211 communique
Patent documentation 4:(Japan) spy opens flat 1-171554 communique
Summary of the invention
The object of the present invention is to provide a kind of high Zeolite formed product that contains promptly to contain the manufacture method of adsorbent formed body and contain the adsorbent formed body by what this manufacture method obtained, its 70 weight % contains zeolite in above high concentration ground, so that hardness is high and can keep absorption affinity.
Even another object of the present invention is to provide a kind of safe and do not use a model respectively, its manufacturing process also is easy to contain the manufacture method of adsorbent formed body.
According to the present invention, a kind of manufacture method that contains the adsorbent formed body can be provided, it is characterized in that having following operation:
Formation contains the operation of the alkoxy silane hydrolyzate of alkoxy silane (silane alkoxide) and hydrochloric acid;
Hydrophobic zeolite is mixed into the operation of this alkoxy silane hydrolyzate;
Making the mixed wetting gel solidification of zeolite that contains is that deformation rate is the operation greater than the wetting gelinite below 0% and 10%;
Cut the operation of this wetting gelinite;
Make wetting gelinite after this cutting dry and form the operation of desiccant gel body;
In addition, according to the present invention, can provide a kind of and contain the adsorbent formed body by what the above-mentioned manufacture method that contains the adsorbent formed body obtained.
As mentioned above, according to the present invention, owing to established easy shaping and can regulate the condition that height contains the wetting gel of zeolite, therefore, even by device such as mixer and comminutor and the high formed body of zeolite containing ratio that uses a model no longer respectively and also can obtain high rigidity.
In addition, in the present invention, as zeolite, owing to use hydrophobic zeolite, therefore, the formed body that is obtained is adsorption moisture organic gas and foul smell in addition efficiently, can be applicable to various purposes.
In addition, as binding agent, by using the binding agent of organic resin; can under the state that keeps hardness, obtain the high formed body of zeolite containing ratio; by using the binding agent of clay based material, can carry out sintering, drying with low temperature, and not use comminutor etc. to form.
Manufacturing method according to the invention, owing to do not use a model respectively and adsorbent can be shaped, therefore, do not have the mould of going into, play modulo operation, can simplify manufacturing process, can reduce, can be made into body with high productivity ratio by the shortcoming, the breakage that work the formed products that is molded as.
The specific embodiment
Below, embodiments of the present invention are described in detail.
In the present invention, adding hydrophobic zeolite and obtain deformation rate in the hydrolyzate of being made by sol-gel process is greater than the wetting gelinite below 0% and 10%.This be because, because in the silica gel alkoxy silane (TEOS) of the gelation () middle and high concentration ground interpolation zeolite difficulty, so need under collosol state, add.
As hydrolyzate of the present invention, must use the alkoxy silane hydrolyzate (colloidal sol) that contains hydrochloric acid and alkoxy silane (TEOS).This be because, in the silane coupling agent hydrolyzate, have zeolite precipitation to produce, the molecular weight height can not disperse zeolite with high concentration in the polysiloxanes and the alkoxysilane oligomer aqueous solution.In addition, when using weak acid such as acetic acid rather than using the strong acid hydrochloric acid that uses in the alkoxy silane hydrolyzate, zeolite produces precipitation.
The content that is used for the alcohol and water of alkoxy silane hydrolyzate solvent be water concentration more than 5 weight %, preferred 20 weight %.When the ratio of the water in the alkoxy silane hydrolyzate solvent increases, shorten up to the time of gelation.This think because, during known alkoxy silane hydrolysis, if water becomes the three-dimensional cancellous SiO bonding polymer in OH Quito at most, and easier gelation when adding hydrophobic zeolite.When water concentration less than 5 weight %, do not carry out the alkoxy silane hydrolysis.In addition,, mix with hydrophobic zeolite even only make the alkoxy silane hydrating solution with alcoholic solvent, can not gelation, can not make wetting gel.
The preferred carbon number of alcohol that is used for alkoxy silane hydrolyzate solvent is below 4, and it is short that the such lower alcohol of methyl alcohol and ethanol reaches the time of gelation.This think because, carbon number owing to the molecular weight height, therefore, has hindered the wetting gelation of hydrophobic zeolite powder and alkoxy silane hydrolysate at the higher alcohol 5 or more.
The concentration of the hydrochloric acid (HCl) that uses as acid catalyst in the alkoxy silane hydrolyzate is preferably (HCl)/(TEOS)=0.01～0.4 with molar ratio computing.When the mol ratio of not enough (HCl)/(TEOS)=0.01, be difficult to carry out the alkoxy silane hydrolysis, when surpassing the mol ratio of (HCl)/(TEOS)=0.4, acid concentration uprises, and handles to become dangerous.When the alkoxy silane hydrolyzate improves in HCl concentration, reach the time lengthening of gelation.Like this, in the HCl catalyst, when alkoxy silane is hydrolyzed, become SiO with OH base
2Therefore linear polymer, can make the wetting gel that contains the hydrophobic zeolite powder.Think when HCl concentration uprises, be hydrolyzed and SiO
2Linear molecule twines mutually, and therefore, even add hydrophobic zeolite, the time that reaches gelation also can be elongated.
When base catalyst is used for the catalyst of alkoxy silane hydrolyzate, after the alkoxy silane hydrolysis, become the few SiO of OH base
2Spherical particle, therefore, even add the hydrophobic zeolite powder also difficulty become wetting gel.
As the collosol concentration of alkoxy silane hydrolyzate, when colloidal sol weight % is too high, when adding, hydrophobic zeolite solidifies, therefore, below the preferred 50 weight % of colloidal sol, as lower limit, during solvent-free composition, be difficult to hydrophobic zeolite is mixed, therefore, more preferably 15～35 weight %.
The alkoxy silane hydrolyzate obtains by at room temperature stirring more than 1 minute, and more than 5 hours, the hardness of formed body uprises by continuous stirring, and is therefore preferred.
In addition, the alkoxy silane hydrolyzate that stirring is obtained left standstill under the room temperature (23 ℃ ± 2 ℃) in 1 above 1 month of week of keeping, and hardness will be higher.
In the present invention, as the zeolite that is added in the alkoxy silane hydrolyzate, must use hydrophobic zeolite.Reason is: usually, when adding,, carry out near the heat release to 200 ℃ afterwards or further when colloidal sol is made, also use strong acid such as hydrochloric acid by the moisture of adsorption of hydrolyzation liquid as the widely used water imbibition zeolite of zeolite, therefore, processing such as operation and security becomes easy.
In addition, the water imbibition zeolite will be controlled the adstante febre that the absorption because of moisture causes, if the water of hydrolyzate is replaced into alcoholic solution, and zeolite precipitation and can not gelation then.
The hydrophobic zeolite of using among the present invention is initiation material with natural zeolite or synthetic zeolite, the method that utilization is modulated by the dealumination treatment of having used inorganic acid etc. etc., or silica source, alumina source, alkali source and organic mineralizer mixed and the acquisitions such as direct synthesis technique of crystallization.Zeolite is the particulate matter of difference according to bulk of molecule employed porous matter during with separating substances, and for having the structure of uniform pore, with enter pore the cavity little Molecular Adsorption and show a kind of effect of sieve, thus, the kind of adsorbable molecule is determined by zeolite type.Under the situation of gas componants such as absorption organic principle, as long as the pore inlet diameter of zeolite than the molecular diameter that is adsorbed greatly.Usually, so long as pore inlet get final product for the zeolite of 8,10 or 12 Yuans rings of oxygen.In the present invention, especially preferably utilize the zeolite of moisture preferential adsorption organic gas and foul smell composition.
When in the alkoxy silane hydrolyzate, adding hydrophobic zeolite,, when adding hydrophobic zeolite in a large number, under the state of powder, be difficult to mix in order to make its content height as shown in the present, in addition, owing to be micropowder, thereby make and go up quantitative difficulty.Therefore, the hydrophobic zeolite powder made mixes with the alkoxy silane hydrolyzate again after the pasty state, thus the quantitative interpolation of hydrophobic zeolite become easily and the processing in the manufacturing easy.In addition, do not become pasty state, thus, can in clean room, handle yet because hydrophobic zeolite is not a powder.Even be added on hydrophobic zeolite in the alkoxy silane hydrolyzate during mixing or the alkoxy silane hydrolyzate be added on also all it doesn't matter in the hydrophobic zeolite.
For hydrophobic zeolite is made pasty state, even making hydrophobic zeolite become pasty state as solvent, can not fully mix water, therefore, water is not suitable for doing solvent.In addition,, when using the such lower alcohol of methyl alcohol and ethanol, be difficult to keep pasty state, therefore, preferably use the low alcohol of volatility such as isopropyl alcohol and butanols because of volatile as solvent.
For the high rigidityization of formed body, need to improve wetting gel strength, therefore, the solvent that hydrophobic zeolite is stuck with paste partly reduces and the hydrophobic zeolite concentration that improves as much as possible in the preferred paste of hydrophobic zeolite concentration is 30 weight %～60 weight %.When surpassing 60 weight %, do not reach the pasty state attitude and have the hydrophobic zeolite powder residual.
Usually, will just begin to become wetting gel after alkoxy silane hydrolyzate and the hydrophobic zeolite mixing, the state that contains the wetting gel of zeolite be as follows:
(1) has the state (state that can not keep shape when flowing in the plane) of moving property;
(2) there is not mobile state (argillaceous) ... rate of change is for surpassing below 10% and 95%;
(3) there is not mobile state (agar shape) ... rate of change is for surpassing below 0% and 10%.
Along with the time changes successively.In the present invention, mixed wetting gel is packed into when having flowability leave standstill in the container so that its state deformation rate that is cured to the no flowability of agar shape is the wetting gelinite that surpasses below 0% and 10%.Deformation rate can reach in the scope of the present invention by time of repose is changed.Use deformation rate to surpass wetting gelinite below 0% and 10%, the processing in the following thus cutting action will be easy, in addition, during microfabrication, can precision cutting profile, size well.
Deformation rate of the present invention is under the environment of 23 ℃/55%RH:
(1) the wetting gelinite that will be configured as diameter 15mm * thickness 5mm is placed on the face of level;
(2) with above-mentioned wetting gelinite with the cylinder of diameter 10mm (raw material: the SUS304 stainless steel) apply the load of 20N;
(3) after discharging 3 seconds, (remove the back), measure the thickness of wetting gelinite, calculate deformation rate by following formula if no longer additional other load then keeps shape:
With deformation rate=(because of the recessed distance of load (mm)/5mm) * 100% expression.
When the solvent composition that contains wetting gelinite for a long time, volume contraction becomes fragile greatly and easily during primary drying, therefore, the gel strength of wetting gelinite preferably more than 30 weight %, preferred especially 45 weight %～80 weight %.In addition, when the hydrophobic zeolite powder is made the pasty state use, use solvent when doing, therefore, need to reduce the solvent composition of alkoxy silane hydrolyzate owing to paste.
Container is not particularly limited, and preferably packs flat container into and forms sheet.With wetting gelinite with the sheet of the no flowability that obtained such as cutter according to purposes be cut into various shapes and make its drying thereafter.In the time of will after following drying means, cutting, with the desiccant gel body broken be powder etc., be difficult to the shape that obtains to require, perhaps when the shape that makes the desiccant gel body was big, it is big that volume contraction becomes, thereby crack sometimes.As shown in the present, by wetting gelinites such as sheet are cut, compare with present method with model, can obtain a large amount of wetting gelinites that requires shape at short notice, can boost productivity.
The formed body that obtains by the present invention is because make the formed body of the absorption affinity that keeps zeolite powder, preferred 70～98 weight % of the content of hydrophobic zeolite, more preferably 80～95 weight %, preferred again 85～95 weight %.By the content that makes hydrophobic zeolite is the formed body of 85～95 weight %, can make to make concave-convex surface minimizing that the deformation rate that becomes before the cutting forming produces when surpassing wetting gel (agar shape) state 0% and 10% below and standard deviation at the good formed body of the dimensional accuracy below 0.01.This thinks, becomes in order to make that deformation rate is reacted when surpassing the wetting gel (agar shape) below 0% and 10% and the collosol and gel composition that changes reduces concave-convex surface.
In addition, in manufacture method of the present invention, before hydrophobic zeolite is mixed, concave-convex surface is reduced, can obtain the good formed body of dimensional accuracy by adding the water system surface conditioner.When making wetting gelinite in that hydrophobic zeolite is mixed into the alkoxy silane hydrolyzate in other words, along with solvent evaporates and alkoxide gelization, produce Bei Naer monomer sample concavo-convex of arc crater (crater) shape sometimes on the surface, therefore, produce uneven aspect the height (thickness) of the formed body of making at the wetting gel of cutting, when making the formed products of fine shape, sometimes reduce dimensional accuracy, but, by in the alkoxy silane hydrolyzate, adding the water system surface conditioner, concave-convex surface is reduced.
The water system surface conditioner can exemplify as main component: contain pure alkane (hydrocarbon) oxygen base thing (alcohol alkoxylate), fluorine and be surfactant, acrylic copolymer, silicone based etc.On the other hand, therefore the surface conditioner of solvent system can not use owing to be insoluble to the alkoxy silane hydrolyzate.With acrylic copolymer, silicone based or fluorine is that surfactant is that the surface conditioner of main component produces small bubble when hydrophobic zeolite is mixed, small bubble remains in the formed body inside after the shaping sometimes, but, make micro-bubble be contained in formed body inside, the surface area that contacts with atmosphere of Zeolite formed product is increased, thereby can realize the raising of adsorption capacity.The small bubble that hydrophobic zeolite produced when mixing with surface that air contacts on fade away, therefore, do not form substantially on the surface of wetting gelinite because of bubble cause concavo-convex, bubble only is present in inside.The ratio of the micro-bubble of formed body inside can be regulated by the addition to surface conditioner, and as foaming capacity, fluorine is the surface conditioner excellence, and is preferred aspect adsorption capacity.Because alcohol alkoxylates does not produce bubble when hydrophobic zeolite is mixed, therefore, formed body inside does not have bubble.Formed body inside does not have bubble and inside to contain micro-bubble to compare, because hydrophobic zeolite is the state that fills up, so its intensity aspect is preferred.
The addition of surface conditioner is with respect to preferred 0.01～1 weight % of alkoxy silane hydrolyzate solid constituent, more preferably 0.1～0.5 weight %.When less than 0.01 weight %, the effect that the concave-convex surface of formed body is reduced is little, on the other hand, and when surpassing 1 weight %, sometimes the absorbability that contains the absorbent formed body is influenced, in addition, be in the surfactant at acrylic copolymer, silicone based and fluorine, bubble sometimes too much and bubble less than reaching body inside, an alveolate part forms concavo-convex situation on the surface, make the height of formed body produce inequality, have, the too much formed body of the ratio of bubble will embrittlement.
Because hydrophobic zeolite containing ratio height of the present invention, promptly binding agent is few, therefore, is difficult to make the formed body that keeps hardness, when making fine shape, needs no brittleness.
Therefore, in the present invention, as the drying means of the wetting gelinite that contains zeolite, the primary drying that preferably is used to make the moisture solvent of gel partly to volatilize makes the hydrophobic zeolite crystallization then and is used to improve the redrying of hardness.In primary drying, because make moisture and the volatilization of pure composition, can make its drying if temperature room temperature (23 ℃ ± 2 ℃) is above, special preferred 23 ℃～120 ℃, more preferably 23 ℃～60 ℃.As drying time, preferred 2 minutes～30 minutes.In redrying, the desiccant gel body is because the SiO in the hydrophobic zeolite
2Not crystallization, thereby hardness is low, therefore, preferably makes its drying more than 140 ℃, and the present invention compares with existing method for making and can make its drying with low temperature more, therefore, as on be limited to below 800 ℃ more preferably 200 ℃～350 ℃.As drying time, preferred 1 hour～3 hours.
(embodiment)
Below, the present invention will be described in more detail to exemplify specific embodiment, but the present invention is not limited to these embodiment.
(embodiment 1-1)
Alkoxy silane (TEOS) 25g
Pure water 23.5g
Methyl alcohol 37.6g
2N hydrochloric acid 7.0g (mol ratio (HCl)/(TEOS)=0.12)
Above-mentioned material is stirred 24 hours making alkoxy silane hydrolyzates (collosol concentration 26.8 weight %) in room temperature (23 ℃).Thereafter, mix with 46.16g hydrophobic zeolite (trade name: HiSiV3000, the clear and society's system of ユ ニ オ Application), in the culture dish of diameter 12cm on the platform of the maintenance level of packing into then, under the environment of 23 ℃/55%RH, leave standstill, contain the wetting gelinite of zeolite (gel strength 45 weight %) in order to the agar shape of the no flowability of the sheet of making thickness 3mm.The deformation rate of the wetting gelinite of the usefulness of making mensuration equally, is 2%.
The wetting gelinite of zeolite that contains that is obtained is cut into after 3 * 3 * 3mm, makes it carry out 5 minutes primary dryings, in order to make the desiccant gel body with 100 ℃.
Then, make the desiccant gel body in electric furnace, carry out 2 hours redryings, obtain the formed body of hydrophobic zeolite containing ratio 80 weight % thus with 300 ℃.
The Zeolite formed product that obtains is estimated according to following evaluation method.Show the result in table 1.
＜estimate
" hardness "
Make the columniform formed body of diameter 2mm * height 3mm, the peak value when utilizing digital force gauge (FGC-50, SHIMPO society system) to measure crushing destruction to the hardness of this formed body.Measured value is for measuring the mean value of times N=7.
" absorption "
For the characterization of adsorption of the gas componant of studying formed body, with the columniform formed body of diameter 2mm * height 3mm with contain in tablet (active constituent content 10%) closed container of packing into of triethylamine, under the environment of 25 ℃/50%RH, placed 240 hours.Thereafter, detecting the triethylamine composition with GC-MS device (Automass, NEC's system) has or not absorption and estimates.Show the result in table 1.
" height-precision (standard deviation) "
Utilize microscope to measure the height (thickness) of the formed body of 3 * 3 * 3mm at three positions, calculate difference in height (maximum-minimum of a value) at a formed body.Carry out this mensuration and calculate standard deviation with 20 formed bodies.
(embodiment 1-2～1-8)
Same with embodiment 1-1, make the alkoxy silane hydrolyzate, as shown in table 1, hydrophobic zeolite containing ratio, hydrolyzate holding time, gel strength, drying condition, time of repose are changed, remove the change deformation rate, be made into body equally and estimate.Show the result in table 1.
(table 1)
| Embodiment 1-1 | Embodiment 1-2 | Embodiment 1-3 | Embodiment 1-4 | Embodiment 1-5 | Embodiment 1-6 | Embodiment 1-7 | Embodiment 1-8 | |
| The zeolite containing ratio | 80 weight % | 80 weight % | 80 weight % | 80 weight % | 80 weight % | 80 weight % | 80 weight % | 80 weight % |
| The TEOS hydrolyzate holding time | 24 hours | 24 hours | 24 hours+2 weeks | 24 hours | 24 hours | 24 hours | 24 hours | 24 hours |
| Deformation rate | 2％ | 2％ | 2％ | 2％ | 1％ | 8％ | 2％ | 2％ |
| Wetting gel strength | 45 weight % | 45 weight % | 45 weight % | 55 weight % | 45 weight % | 45 weight % | 45 weight % | 45 weight % |
| The primary drying condition | With 100 ℃ 5 minutes | With 100 ℃ 5 minutes | With 100 ℃ 5 minutes | With 100 ℃ 5 minutes | With 100 ℃ 5 minutes | With 100 ℃ 5 minutes | With 25 ℃ 15 minutes | With 60 ℃ 10 minutes |
| The redrying condition | With 300 ℃ 2 hours | Do not have | With 300 ℃ 2 hours | With 300 ℃ 2 hours | With 300 ℃ 2 hours | With 300 ℃ 2 hours | With 300 ℃ 2 hours | With 300 ℃ 2 hours |
| Hardness (N) | 4.41 | 2.57 | 6.81 | 10.72 | 4.36 | 4.46 | 4.33 | 4.42 |
| Trimethylamine absorption | Have | Have | Have | Have | Have | Have | Have | Have |
| Height-precision (standard deviation) | 0.013 | 0.013 | 0.013 | 0.013 | 0.013 | 0.013 | 0.013 | 0.013 |
(embodiment 2-1～2-3)
Same with embodiment 1-1, make the alkoxy silane hydrolyzate, as shown in table 2, remove the change hydrophobic zeolite containing ratio, be made into body equally and estimate.Show the result in table 2.
(table 2)
| Embodiment 2-1 | Embodiment 2-2 | Embodiment 2-3 | |
| The hydrophobic zeolite containing ratio | 70 weight % | 85 weight % | 90 weight % |
| Wetting gel strength | 45 weight % | 50 weight % | 59 weight % |
| Deformation rate | 2％ | 2％ | 2％ |
| Hardness (N) | 2.76 | 7.03 | 9.69 |
| Trimethylamine absorption | Have | Have | Have |
| Height-precision (standard deviation) | 0.015 | 0.004 | 0.002 |
As shown in Table 2, become more than the 85 weight %, reduce concave-convex surface by making the hydrophobic zeolite amount, can obtain standard deviation 0.01 below with the good formed body of height-precision.This is by observing concave-convex surface with microscope (150 times), hydrophobic zeolite amount for embodiment 2-1 is the formed body of 70 weight %, the concavo-convex of arc crater shape can be seen in the surface, but for the formed body of embodiment 2-2 and 2-3, then can't see concavo-convex also can be clear.
(embodiment 3-1)
Same with embodiment 1-1, make the alkoxy silane hydrolyzate.What add 0.01g in this alkoxy silane hydrolyzate is the surface conditioner (trade name: BYK-DYNWET800, テ Star ニ system) of main component with the alcohol alkoxylates.Thereafter, with the 46.16g hydrophobic zeolite (trade name: HiSiV3000) mix and embodiment 1-1 same, be made into body and estimate.
Also have, aspect evaluation,, utilize the measured value of the CG-MS device that in absorption, uses to estimate in order to study the adsorption capacity of triethylamine.Evaluation method is for to compare with the adsorption capacity of embodiment 1-1,1.1 times of less thaies: note is made △, and more than 1.1 times, be lower than 1.5 times: note is done more than zero, 1.5 times: note is made ◎.In addition, as the state of formed body, utilize microscope (10 times) to observe and cut into the section behind the body and observe the state of bubble with cutting machine.Show the result in table 3.
(embodiment 3-2～3-11)
In embodiment 3-1, as shown in table 3, with surface conditioner change silicone based (trade name: デ イ ス パ ロ Application, nanmu originally change into system) into, fluorine is surfactant (trade name: メ ガ Off ア Star Network, big Japanese イ Application キ system), acrylic copolymer (trade name: BYK-381, テ Star ニ system), except that changing addition, be made into body equally and estimate, show the result in table 3.
As shown in Table 3, reduce concave-convex surface, can obtain standard deviation below 0.01 and the good formed body of height-precision by surface conditioner is added in the alkoxy silane hydrolyzate.In addition, when observing concave-convex surface,, can see mild concavo-convex in the part on surface for the formed body of embodiment 3-1,3-3～3-5,3-7,3-8,3-11 with microscope (150 times), but, then can't see concavo-convex for the formed body of embodiment 3-2,3-6,3-9,3-10.
(embodiment 4-1)
Alkoxy silane (TEOS) 25g
Pure water 20g
2N hydrochloric acid 5g (mol ratio (HCl)/(TEOS)=0.08)
Above-mentioned material is stirred 24 hours making alkoxy silane hydrolyzates (collosol concentration 50 weight %) with room temperature (23 ℃).Thereafter, with 46.16g isopropyl alcohol and 46.16g hydrophobic zeolite (trade name: HiSiV) mix and make hydrophobic zeolite and stick with paste (zeolite concentration is 50 weight %).Adding hydrophobic zeolite in the alkoxy silane hydrolyzate sticks with paste and stirs, in the culture dish of diameter 12cm on the platform of the maintenance level of packing into, under the environment of 23 ℃/55%RH, leave standstill, make thickness 3mm sheet no flowability the agar shape contain the wetting gelinite of zeolite (gel strength 40.5 weight %).Equally, the deformation rate of the wetting gelinite of the mensuration usefulness of made is 2%.
The wetting gelinite of zeolite that contains that is obtained is cut into after 3 * 3 * 3mm, makes it carry out 15 minutes primary dryings, make the desiccant gel body with 25 ℃.
Then, make the desiccant gel body in electric furnace, carry out 2 hours redryings, can obtain the formed body of hydrophobic zeolite containing ratio 80 weight % thus with 300 ℃.
The Zeolite formed product and the embodiment 1-1 that obtain are estimated equally.Show the result in table 4.
(embodiment 4-2～4-3)
In embodiment 4-1, the hydrophobic zeolite when changing making hydrophobic zeolite paste and the mixing ratio of isopropyl alcohol, except that with zeolite concentration be 30 weight % instead of embodiment 4-2, with zeolite concentration be 60 weight % instead of the embodiment 4-3, similarly be made into body and estimate.Show the result in table 4.
(embodiment 4-4)
In embodiment 4-1, when make sticking with paste, remove 65.6g hydrophobic zeolite and 65.6g isopropyl alcohol are mixed, make hydrophobic zeolite and stick with paste (zeolite concentration is 50 weight %) in addition, to make the hydrophobic zeolite containing ratio equally be the formed body of 85 weight % and estimate.Show the result in table 4.
(embodiment 4-5)
In embodiment 4-1, when make sticking with paste, remove 104g hydrophobic zeolite and 104g isopropyl alcohol are mixed, make hydrophobic zeolite and stick with paste (zeolite concentration is 50 weight %) in addition, to make the hydrophobic zeolite containing ratio equally be the formed body of 90 weight % and estimate.Show the result in table 4.
(embodiment 4-6～4-7)
In embodiment 4-5, the hydrophobic zeolite when changing making hydrophobic zeolite paste and the mixing ratio of isopropyl alcohol, except that with zeolite concentration be 30 weight % instead of embodiment 4-5, with zeolite concentration be 60 weight % instead of the embodiment 4-6, be made into body equally and estimate.Show the result in table 4.
(table 4)
| Embodiment 4-1 | Embodiment 4-2 | Embodiment 4-3 | Embodiment 4-4 | Embodiment 4-5 | Embodiment 4-6 | Embodiment 4-7 | |
| The hydrophobic zeolite containing ratio | 80 weight % | 80 weight % | 80 weight % | 85 weight % | 90 weight % | 90 weight % | 90 weight % |
| Hydrophobic zeolite concentration in the paste | 50 weight % | 30 weight % | 60 weight % | 50 weight % | 50 weight % | 30 weight % | 60 weight % |
| Wetting gel strength | 40.5 weight % | 40.5 weight % | 40.5 weight % | 40.5 weight % | 40.5 weight % | 40.5 weight % | 40.5 weight % |
| Deformation rate | 2％ | 2％ | 2％ | 2％ | 2％ | 2％ | 2％ |
| Hardness (N) | 4.40 | 4.36 | 4.46 | 7.05 | 9.69 | 9.64 | 9.75 |
| Trimethylamine absorption | Have | Have | Have | Have | Have | Have | Have |
| Height-precision (standard deviation) | 0.013 | 0.013 | 0.013 | 0.004 | 0.002 | 0.002 | 0.002 |
Can reduce concave-convex surface more than becoming 85 weight % by making hydrophobic zeolite content even use hydrophobic zeolite to stick with paste also, obtain standard deviation below 0.01 with the good formed body of height-precision.In addition, when the zeolite concentration in hydrophobic zeolite is stuck with paste increased, the solvent in the paste partly reduced, therefore, and the trend that as seen has hardness to increase.
(comparative example 1)
Same with embodiment 1-1, make the alkoxy silane hydrolyzate, thereafter, mixes with hydrophobic zeolite, obtain not have flowability the agar shape contain the wetting gelinite of zeolite.The deformation rate of the wetting gelinite that is obtained is 2%.
Not with the diameter 12cm that obtained contain the wetting gelinite cutting of zeolite, and it is carried out 5 minutes primary dryings with 100 ℃, make the desiccant gel body, but because of volume contraction, so before cutting, on the desiccant gel body, crack, and can not be shaped.
(comparative example 2)
In comparative example 1, make with the desiccant gel body of primary drying again in electric furnace with 300 ℃ of desiccant gel bodies that carry out 2 hours redryings, but because of volume contraction, so before cutting, on the desiccant gel body, crack, and can not be shaped.
(comparative example 3)
Alkoxy silane (TEOS) 25g
Pure water 23.5g
Methyl alcohol 37.6g
2N hydrochloric acid 7.0g
Above-mentioned material is stirred 24 hours making alkoxy silane hydrolyzates with room temperature (23 ℃).With 46.16g water imbibition zeolite (3A) mix (gel strength be 45%) thereafter.Near the heat release to 200 at once ℃, before shaping, be cured after the mixing at once.
(comparative example 4)
In comparative example 3, in order to suppress heat release, not pure water but the purpose of alcohol moiety increment to reach to make, except that the methyl alcohol in the hydrolyzate being made 86g, similarly make.With 46.16g water imbibition zeolite (3A) mix (gel strength be 29%) thereafter.Though mixed heat release is suppressed, not gelation and precipitating down.
(comparative example 5)
Aminopropyl trimethoxysilane silane coupler (APTMS) 15g
Methyl alcohol 120g
Ethylene glycol diglycidylether 2g
Above-mentioned material is stirred 24 hours making hydrolyzates with room temperature (23 ℃)., with 16.4g hydrophobic zeolite (HiSiV) mix (gel strength be 22%), not gelation and precipitating down thereafter.
(comparative example 6)
In comparative example 3, except that acetic acid replaces hydrochloric acid, similarly make hydrolyzate, thereafter, mix with 46.16g water imbibition zeolite (3A) (gel strength is 45%), but not gelation and precipitating down.
Manufacturing method according to the invention can be shaped and not use a model respectively to contain adsorbent, and with high productivity ratio, meets the shape of purposes with the high accuracy manufacturing, can be in the adsorbing domain extensive use.
Claims (19)
1, a kind of manufacture method that contains the adsorbent formed body is characterized in that, has following operation:
Formation contains the operation of the alkoxy silane hydrolyzate of alkoxy silane and hydrochloric acid;
Hydrophobic zeolite is mixed into operation in this alkoxy silane hydrolyzate;
Making the mixed wetting gel solidification of zeolite that contains is that deformation rate is the operation that surpasses the wetting gelinite below 0% and 10%;
Cut the operation of this wetting gelinite;
Make wetting gelinite after this cutting dry and form the operation of desiccant gel body.
2, the manufacture method that contains the adsorbent formed body as claimed in claim 1 is characterized in that, the mode that becomes 70～98 weight % with the hydrophobic zeolite containing ratio of described desiccant gel body forms.
3, the manufacture method that contains the adsorbent formed body as claimed in claim 2 is characterized in that, the mode that becomes 80～95 weight % with the hydrophobic zeolite containing ratio of described desiccant gel body forms.
4, as each described manufacture method that contains the adsorbent formed body in the claim 1～3, it is characterized in that the solvent as described alkoxy silane hydrolyzate contains alcohol and water, the content of water is more than the 5 weight %.
5, as each described manufacture method that contains the adsorbent formed body in the claim 1～4, it is characterized in that the carbon number of the alcohol of described alkoxy silane hydrolyzate solvent is below 4.
6, as each described manufacture method that contains the adsorbent formed body in the claim 1～5, it is characterized in that the concentration of the hydrochloric acid (HCl) of described alkoxy silane (TEOS) hydrolyzate that contains hydrochloric acid is (HCl)/(TEOS)=0.01～0.4 with molar ratio computing.
7, as each described manufacture method that contains the adsorbent formed body in the claim 1～6, it is characterized in that before the operation that described hydrophobic zeolite is mixed, also having the operation of adding the water system surface conditioner.
8, the manufacture method that contains the adsorbent formed body as claimed in claim 7 is characterized in that, described water system surface conditioner is an alcohol alkoxylates.
9, the manufacture method that contains the adsorbent formed body as claimed in claim 7 is characterized in that, described water system surface conditioner is that fluorine is a surfactant.
As each described manufacture method that contains the adsorbent formed body in the claim 1～9, it is characterized in that 10, the addition of described water system surface conditioner is 0.01～1 weight % with respect to alkoxy silane hydrolyzate solid constituent.
As each described manufacture method that contains the adsorbent formed body in the claim 1～10, it is characterized in that 11, this hydrophobic zeolite of mixing in the operation of described hydrophobic zeolite is a pasty state.
12, the manufacture method that contains the adsorbent formed body as claimed in claim 11 is characterized in that, the hydrophobic zeolite of the described pasty state paste that mixes with isopropyl alcohol of serving as reasons.
13, as each described manufacture method that contains the adsorbent formed body in the claim 1～12, it is characterized in that, form baking temperature in the operation of described desiccant gel body at 23 ℃～120 ℃ primary drying.
14, as each described manufacture method that contains the adsorbent formed body in the claim 1～13, it is characterized in that also having and make described desiccant gel body in the operation of carrying out redrying more than 140 ℃.
15, the manufacture method that contains the adsorbent formed body as claimed in claim 14 is characterized in that, the temperature of described redrying is 200 ℃～350 ℃.
16, as each described manufacture method that contains the adsorbent formed body in the claim 1～15, it is characterized in that also having described alkoxy silane hydrolyzate is carried out a week above one month operation with interior keeping.
As each described manufacture method that contains the adsorbent formed body in the claim 1～16, it is characterized in that 17, the collosol concentration of described alkoxy silane hydrolyzate is below the 50 weight %.
As each described manufacture method that contains the adsorbent formed body in the claim 1～17, it is characterized in that 18, the gel strength of described wetting gelinite is more than the 30 weight %.
19, a kind of adsorbent formed body that contains is characterized in that, the manufacture method that contains the adsorbent formed body by each record in the claim 1～18 obtains.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP065848/2006 | 2006-03-10 | ||
| JP2006065848 | 2006-03-10 | ||
| JP110846/2006 | 2006-04-13 | ||
| JP144166/2006 | 2006-05-24 | ||
| JP352048/2006 | 2006-12-27 | ||
| JP054227/2007 | 2007-03-05 |
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| Publication Number | Publication Date |
|---|---|
| CN101400440A true CN101400440A (en) | 2009-04-01 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107335495A (en) * | 2017-06-08 | 2017-11-10 | 全椒县崇明米业有限公司 | A kind of big rice processing method for reducing content of cracking rice |
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2007
- 2007-03-07 CN CNA2007800086335A patent/CN101400440A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107335495A (en) * | 2017-06-08 | 2017-11-10 | 全椒县崇明米业有限公司 | A kind of big rice processing method for reducing content of cracking rice |
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