CN1986046B - Preparing process of composite block adsorbent of molecular sieve and modified silica gel - Google Patents
Preparing process of composite block adsorbent of molecular sieve and modified silica gel Download PDFInfo
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- CN1986046B CN1986046B CN2006101237630A CN200610123763A CN1986046B CN 1986046 B CN1986046 B CN 1986046B CN 2006101237630 A CN2006101237630 A CN 2006101237630A CN 200610123763 A CN200610123763 A CN 200610123763A CN 1986046 B CN1986046 B CN 1986046B
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 76
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003463 adsorbent Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 31
- 230000008569 process Effects 0.000 title description 3
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 34
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000919 ceramic Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000835 fiber Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000007731 hot pressing Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 239000001110 calcium chloride Substances 0.000 claims description 11
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical group [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 238000007605 air drying Methods 0.000 abstract description 17
- 230000008929 regeneration Effects 0.000 abstract description 9
- 238000011069 regeneration method Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 4
- 238000010408 sweeping Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 26
- 239000000741 silica gel Substances 0.000 description 25
- 229910002027 silica gel Inorganic materials 0.000 description 25
- 229960001866 silicon dioxide Drugs 0.000 description 25
- 239000004033 plastic Substances 0.000 description 24
- 230000000694 effects Effects 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 230000001413 cellular effect Effects 0.000 description 12
- -1 aluminum modified silica gel Chemical class 0.000 description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 9
- 238000011010 flushing procedure Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- 229910052571 earthenware Inorganic materials 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000004310 lactic acid Substances 0.000 description 5
- 235000014655 lactic acid Nutrition 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 101100468589 Arabidopsis thaliana RH30 gene Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910013500 M-O—Si Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002385 metal-ion deposition Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
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Abstract
The preparation process of composite block adsorbent of molecular sieve and modified silica gel includes the following steps: soaking ceramic fiber paper in water glass and hot pressing to form corrugated paper, adhering to flat sheet paper through the soaking at the same condition to form honeycomb block, drying, soaking the block into metal salt solution to react, washing with clear water, soaking the block in mixed liquid comprising silica sol and molecular sieve, taking out, sweeping to eliminate liquid and air drying to obtain the adsorbent. The adsorbent has homogeneous distribution of adsorbent grains on the base material, high adsorption amount, low regeneration temperature and high heat stability, and is suitable for adsorbing dehumidifying and whole heat recovery at different humidity and/or different temperature.
Description
Technical field
The present invention relates to gas absorption formula dry decontamination and heat recovery technology, particularly the preparation method of molecular sieve and modified silica-gel composite block adsorbent.
Background technology
Ceramic fibre and adsorbent organically combine and construct the cellular block adsorbent that forms, and can be used as dehumidifying changes core, is applied in absorption type desiccant wheel and the full heat recovery system.The adsorbent that changes core as dehumidifying mainly contains silica gel, molecular sieve etc., and they respectively have pluses and minuses.Silica gel has adsorbance preferably, regeneration temperature lower (150 ℃), and its shortcoming is that adsorbance is little under low humidity or higher temperature; Its heat endurance is relatively poor simultaneously, and when at the higher temperature repeated regeneration, fusion, collapse phenomenon easily take place the porous material of non-ordered structure, and its specific area is reduced; The characteristics of molecular sieve are that water is had great affinity, have bigger adsorption capacity when low and temperature is higher at air moisture content, and deficiency is a regeneration energy consumption height (250 ℃).
Disclose in the ZL02149717.6 patent of invention that a kind of " " preparation method of nano aperture silica gel absorber and application thereof " propose to add the method for modifying that soluble calcium salt is made precipitating reagent, and the result shows, can significantly improve the silica gel growing amount." aluminum modified silica gel adsorbent material and preparation method thereof ", " titanium modified silica-gel adsorbent block preparation method " are disclosed respectively in number of patent application is 200410050867.4 and 200510033982.5 patent of invention, by in acid solution, adding the method for aluminum soluble salt or titanium salt, on the inorganic fibre paper of hydrated glass, flood codeposition, obtain aluminum modified silica or titanium modified silica-gel block adsorbent, its absorption property, thermal stability significantly strengthen.In above-mentioned patent, although the silica gel after improvement or the modification makes moderate progress at absorption property, thermal stability, the change of essence does not still take place in the absorption property under low humidity or higher temperature.In the US4886769 patent, disclose a kind of " active gases absorbing unit and manufacture method ", wherein adopted waterglass to make the dispersant and the adhesive of molecular sieve, made molecular sieve silicate adsorbent.Because this adsorbent combines the characteristics separately of molecular sieve and silica gel, its absorption property significantly strengthens, and the scope of application is widened (can use) under low humidity, higher temperature environmental condition.But, find in the real process that there is molecular sieve bad dispersibility in waterglass in this method, deposition defective such as inhomogeneous on fiber simultaneously because of the waterglass strong basicity, easily produces destruction to the inherent structure of molecular sieve, thereby influences the absorption property of compound adsorbent.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of adsorbance bigger, regeneration temperature is lower, the preparation method of thermally-stabilised molecular sieve preferably and modified silica-gel composite block adsorbent, the adsorbent that obtains can be used for absorption type rotary wheel dehumidifying or the full recuperation of heat under different humidity, the different temperatures environmental aspect.
The preparation method of molecular sieve of the present invention and modified silica-gel composite block adsorbent may further comprise the steps:
(1) ceramic fiber paper is flooded in waterglass after hot-forming corrugated paper, be bonded into cellular block, be cooled to room temperature after the drying with the sheet paper of the same terms steep water glass;
(2) in 10～30% quality metal salt solutions, add acid solution regulator solution pH value to 0.5～2.5, be warming up to 60 ℃, stir, the block of step (1) preparation is immersed wherein, reaction finish the back with the clear water flushing to neutral modified silica-gel block;
(3) the modified silica-gel block with step (2) preparation is immersed in the mixed liquor of being made up of Ludox and molecular sieve, and the pH value of mixed liquor is controlled at 8.5～9.5, stirs, take out the modified silica-gel block, liquid purge also dries, and drying gets molecular sieve and modified silica-gel composite block adsorbent.
In the step (1), the preferred modulus of waterglass is 3.5, and concentration is the waterglass of 20% quality.
In the step (2), described slaine is titanium sulfate, titanyl sulfate; Aluminum sulfate, aluminium chloride; Calcium chloride, calcium nitrate; In magnesium nitrate, the magnesium chloride one or more.
Slaine can be single salt in the described step (2), also can be two or more metal mixed salt.These salt mainly comprise titanium sulfate, titanyl sulfate; Aluminum sulfate, aluminium chloride; Calcium chloride, calcium nitrate; Magnesium nitrate, magnesium chloride or the like.On the principle, compound between different metal salt, Several combination is arranged, under the certain prerequisite of complex salt total concentration, their different quality proportionings, capable of being combined again some, for simplifying experiment, mass ratioes such as their employings are mixed.The experiment proved that following several salt mixed effect is better: aluminum sulfate and titanyl sulfate; Aluminium chloride and calcium chloride; And aluminum sulfate, titanyl sulfate and calcium chloride etc.
In the step (2), described metal salt solution concentration is 5%～30% quality.Salinity is too low, and the metal ion deposition is few, and salinity is too high, then deposits inhomogeneously, and matched proportion density is 10%～25% preferably.
In the step (3), described Ludox average grain diameter is 8～25nm, and its concentration is 10～30% quality.
In the step (3), molecular sieve is the synthesis of molecular sieve powder, and average grain diameter is 2～5 μ m, and its consumption accounts for 10～50% of Ludox quality.
PH value of solution value described in the described step (2) is preferred 0.5～2, when selecting acid to regulate salting liquid pH value, can be strong acid (as sulfuric acid, hydrochloric acid etc.), also can be weak acid (as acetic acid, lactic acid etc.), the need Consideration:
Acid solution is to the corrosivity of cellular block, and pH value amplitude of variation (the pH value is minor swing as far as possible) should use low concentration weak acid to regulate the pH value in the reaction system.
Ludox is alkalescent colloid (pH value is 8.5～9.5) in the described step (3), during use, and the product of prepared fresh preferably, overlong time, the increase of colloidal sol particle diameter, even phenomenons such as layering, deposition appear.The Ludox average grain diameter is preferably 15～25nm, and its concentration is preferably 10～25%.Thickness of silica gel is low excessively, and its viscosity is less, and the amount of bonding molecular sieve is little on ceramic fibre, and the compound adsorbance is little; And too high thickness of silica gel can cause the Ludox on ceramic fibre scraps of paper surface to increase, and can part block up sieve in the hole of molecular sieve, silica gel, thereby influence the absorption property of compound adsorbent.
Molecular sieve is artificial synthesis of molecular sieve powder in the described step (3), as model molecular sieves such as 3A, 4A, 5A, 13X.During use, earlier molecular sieve is sieved, its average grain diameter is preferably 2～4 μ m, along with the molecular sieve addition increases, the adsorbance of adsorbent increases, but too much molecular sieve needs stronger bonding force, and makes the ceramic fibre scraps of paper produce bad phenomenon such as distortion, molecular sieve dry linting.Its consumption is preferably and accounts for 15～30% of Ludox quality.
The present invention adopts on ceramic fibre successively steep water glass, acidic salt solution and contains the molecular sieve Ludox, by codeposition and composite methods, make space and the surface of the molecular sieve/modified silica-gel compound uniform deposition of generation at ceramic fibre, handle through washing, oven dry again, thereby synthesize high adsorption capacity, low regeneration temperature, the better molecular sieve/modified silica-gel composite block adsorbent of heat resistance; Prepared adsorbent can be applicable to the full heat regenerator of absorption type desiccant wheel.
Adopt the inventive method based on following operation principle:
At first, with the ceramic fiber paper is base material, by immersion deposition and composite methods, adsorbent is dispersed on the ceramic matrix, and is processed into cellular block, owing to adopt original position to generate and combination process, adsorbent and ceramic fibre effect are strong, when the adsorbent repeated regeneration, heat partly can be transferred on the resistant to elevated temperatures ceramic fiber paper, can to a certain degree improve the service life of adsorbent.
Secondly, by the method for metal ion mixing, silica gel is carried out modification, because metal ion mixing changes the adsorbent surface structure, improve silica gel specific area and pore volume, and form Heat stability is good M-O-Si key on its surface,, thereby can improve absorption property, the heat endurance of silica gel itself.
At last, adopting Ludox to make the dispersant and the adhesive of molecular sieve powder, is that its dispersion effect better (is seen Fig. 1 because its dispersion effect is than adopting the waterglass that plays identical effect among the patent US4886769 to compare, Fig. 2), can reduce the corrosivity of waterglass simultaneously to Molecular Sieve Pore.Adopting molecular sieve is because compound adsorbent can be in conjunction with the advantage of various adsorbents with the compound of modified silica-gel, also overcome simultaneously the shortcoming and defect of single adsorbent, make it all have and improve (comprising adsorbance, regeneration temperature etc. under different humidity, the non-equality of temperature condition) in absorption property, heat endurance.
The present invention has following advantage and effect with respect to prior art: (1) absorbent particles is uniformly dispersed on ceramic fibre (comparing with the US4886769 patent), thereby the molecular sieve difficult drop-off, and processability is good; (2) no matter be low humidity, or high humidity, the composite block adsorbent absorption property obviously be better than silica gel product of the same type (with the ZL02149717.6 patent relatively); (3) heat resistance good (comparing) with silica gel; (4) under the prerequisite of identical moisture removal, composite block adsorbent is compared with molecular sieve or silica gel block, needs lower regeneration temperature.
Description of drawings
Fig. 1 is the optical microscope photograph figure of molecular sieve in different dispersants;
Fig. 2 is the adsorbent SEM figure of the inventive method preparation under the different dispersants;
Fig. 3 is adsorbent absorption property comparative graph under different relative humidity of the inventive method preparation;
Fig. 4 is the absorption property curve map of the adsorbent of the inventive method preparation under the Different Silicon collosol concentration;
Attached dose absorption property curve map of the inventive method preparation under Fig. 5 different molecular sieve amount;
Attached dose absorption property curve map of the inventive method preparation under Fig. 6 different metal salt.
The specific embodiment
Embodiment 1
(1) under the room temperature, in 20L square plastic container, add 2.5L water, add modulus then and be 3.5, concentration 25% waterglass 10kg, after stirring, ceramic fiber paper is immersed wherein, take out drying behind the 20min, on the corrugated paper machine, be rolled into corrugated, and with bonding under the effect of waterglass with quadrat method dipping earthenware slab paper, be made into the ceramic honeycomb block (100 * 100 * 100mm), at 120 ℃ of following forced air drying 8h, be cooled to room temperature then;
(2) in 20L square plastic container, take by weighing 1.5kg titanyl sulfate and 1.5kg aluminum sulfate respectively and be dissolved in the water of 12L, add acetic acid regulator solution pH value 1.0, be warming up to 60 ℃, under brute force stirs, above-mentioned cellular block is immersed wherein, and strict control pH value is (along with the carrying out of reaction, the pH value of solution value raises, need add acid solution frequently, as follows), take out after 6 hours, with the clear water flushing, dry;
(3) get 25L square plastic container in addition, add 20% silicon sol solution 15L, under mechanical agitation, add 13X molecular sieve 3kg, after mixing, the modified silica-gel block is slowly immersed wherein, take out liquid purge behind the 30min and dry 2hr,, promptly get molecular sieve and modified silica-gel composite block adsorbent at 150 ℃ of following forced air drying 10hr.
(1) under the room temperature, in 20L square plastic container, add 2.5L water, add modulus then and be 3.5, concentration 25% waterglass 10kg, after stirring, ceramic fiber paper is immersed wherein, take out drying after 20 minutes, on the corrugated paper machine, be rolled into corrugated, and with bonding under the effect of waterglass with the earthenware slab paper of quadrat method dipping, be made into the ceramic honeycomb block (100 * 100 * 100mm), at 120 ℃ of following forced air drying 8h, be cooled to room temperature then;
(2) in 20L square plastic container, taking by weighing 1.5kg titanyl sulfate and 1.5kg aluminum sulfate respectively is dissolved in the water of 12L, add lactic acid regulator solution pH value 1.2, be warming up to 60 ℃, under brute force stirs, above-mentioned cellular block immersed wherein, and strict control pH value, take out after 6 hours,, dry with the clear water flushing;
(3) get 25L square plastic container in addition, add 10% silicon sol solution 15L, under mechanical agitation, add 13X molecular sieve 3kg, after mixing, the modified silica-gel block is slowly immersed wherein, take out liquid purge behind the 30min and dry 2hr,, promptly get molecular sieve and modified silica-gel composite block adsorbent at 150 ℃ of following forced air drying 10hr.
(1) under the room temperature, in 20L square plastic container, add 2.5L water, add modulus then and be 3.5, concentration 25% waterglass 10kg, after stirring, ceramic fiber paper is immersed wherein, take out drying after 20 minutes, on the corrugated paper machine, be rolled into corrugated, and with bonding under the effect of waterglass with the earthenware slab paper of quadrat method dipping, be made into the ceramic honeycomb block (100 * 100 * 100mm), at 120 ℃ of following forced air drying 8h, be cooled to room temperature then;
(2) in 20L square plastic container, taking by weighing 1.5kg titanium sulfate and 1.5kg aluminum sulfate respectively is dissolved in the water of 12L, add acetic acid regulator solution pH value 0.8, be warming up to 60 ℃, under brute force stirs, above-mentioned cellular block immersed wherein, and strict control pH value, take out after 6 hours,, dry with the clear water flushing;
(3) get 25L square plastic container in addition, add 25% silicon sol solution 15L, under mechanical agitation, add 13X molecular sieve 3kg, after mixing, the modified silica-gel block is slowly immersed wherein, take out liquid purge behind the 30min and dry 2hr,, get molecular sieve and modified silica-gel composite block adsorbent at 150 ℃ of following forced air drying 10hr.
Embodiment 4
(1) under the room temperature, in 20L square plastic container, add 2.5L water, add modulus then and be 3.5, concentration 25% waterglass 10kg, after stirring, ceramic fiber paper is immersed wherein, take out drying after 20 minutes, on the corrugated paper machine, be rolled into corrugated, and with bonding under the effect of waterglass with the earthenware slab paper of quadrat method dipping, be made into the ceramic honeycomb block (100 * 100 * 100mm), at 120 ℃ of following forced air drying 8h, be cooled to room temperature then; (2) in 20L square plastic container, taking by weighing 1.5kg aluminium chloride and 1.5kg calcium chloride respectively is dissolved in the water of 15L, add lactic acid regulator solution pH value 1.5, be warming up to 60 ℃, under brute force stirs, above-mentioned cellular block immersed wherein, and strict control pH value, take out after 6 hours,, dry with the clear water flushing; (3) get 25L square plastic container in addition, add 20% silicon sol solution 15L, under mechanical agitation, add 5A molecular sieve 1.5kg, after mixing, the modified silica-gel block is slowly immersed wherein, take out liquid purge behind the 30min and dry 2hr,, promptly get molecular sieve and modified silica-gel composite block adsorbent at 150 ℃ of following forced air drying 10hr.
(1) under the room temperature, in 20L square plastic container, add 2.5L water, add modulus then and be 3.5, concentration 25% waterglass 10kg, after stirring, ceramic fiber paper is immersed wherein, take out drying after 20 minutes, on the corrugated paper machine, be rolled into corrugated, and with bonding under the effect of waterglass with the earthenware slab paper of quadrat method dipping, be made into the ceramic honeycomb block (100 * 100 * 100mm), at 120 ℃ of following forced air drying 8h, be cooled to room temperature then;
(2) in 20L square plastic container, taking by weighing 1.5kg magnesium chloride and 1.5kg calcium chloride respectively is dissolved in the water of 15L, add acetic acid regulator solution pH value 2.0, be warming up to 60 ℃, under brute force stirs, above-mentioned cellular block immersed wherein, and strict control pH value, take out after 6 hours,, dry with the clear water flushing;
(3) get 25L square plastic container in addition, add 20% silicon sol solution 15L, under mechanical agitation, add 5A molecular sieve 4.5kg, after mixing, the modified silica-gel block is slowly immersed wherein, take out liquid purge behind the 30min and dry 2hr,, get molecular sieve and modified silica-gel composite block adsorbent at 150 ℃ of following forced air drying 10hr.
(1) under the room temperature, in 20L square plastic container, add 2.5L water, add modulus then and be 3.5, concentration 25% waterglass 10kg, after stirring, ceramic fiber paper is immersed wherein, take out drying after 20 minutes, on the corrugated paper machine, be rolled into corrugated, and with bonding under the effect of waterglass with the earthenware slab paper of quadrat method dipping, be made into the ceramic honeycomb block (100 * 100 * 100mm), at 120 ℃ of following forced air drying 8h, be cooled to room temperature then;
(2) in 20L square plastic container, taking by weighing 1.5kg aluminium chloride and 1.5kg calcium chloride respectively is dissolved in the water of 15L, add acetic acid regulator solution pH value 1.5, be warming up to 60 ℃, under brute force stirs, above-mentioned cellular block immersed wherein, and strict control pH value, take out after 6 hours,, dry with the clear water flushing;
(3) get 25L square plastic container in addition, add 20% silicon sol solution 15L, under mechanical agitation, add 5A molecular sieve 3kg, after mixing, the modified silica-gel block is slowly immersed wherein, take out liquid purge behind the 30min and dry 2hr,, get molecular sieve and modified silica-gel composite block adsorbent at 150 ℃ of following forced air drying 10hr.
Embodiment 7
(1) under the room temperature, in 20L square plastic container, add 2.5L water, add modulus then and be 3.5, concentration 25% waterglass 10Kg, after stirring, ceramic fiber paper is immersed wherein, take out drying after 20 minutes, on the corrugated paper machine, be rolled into corrugated, and with bonding under the effect of waterglass with the earthenware slab paper of quadrat method dipping, be made into the ceramic honeycomb block (100 * 100 * 100mm), at 120 ℃ of following forced air drying 8h, be cooled to room temperature then;
(2) in 20L square plastic container, take by weighing the 3kg titanyl sulfate respectively and be dissolved in the water of 15L, add lactic acid regulator solution pH value 1.5, be warming up to 60 ℃, under brute force stirs, above-mentioned cellular block is immersed wherein, and strict control pH value, take out after 6 hours,, dry with the clear water flushing;
(3) get 25L square plastic container in addition, add 20% silicon sol solution 15L, under mechanical agitation, add 13X molecular sieve 3kg, after mixing, the modified silica-gel block is slowly immersed wherein, take out liquid purge behind the 30min and dry 2hr,, get molecular sieve and modified silica-gel composite block adsorbent at 150 ℃ of following forced air drying 10hr.
(1) under the room temperature, in 20L square plastic container, add 2.5L water, add modulus then and be 3.5, concentration 25% waterglass 10Kg, after stirring, ceramic fiber paper is immersed wherein, take out drying after 20 minutes, on the corrugated paper machine, be rolled into corrugated, and with bonding under the effect of waterglass with the earthenware slab paper of quadrat method dipping, be made into the ceramic honeycomb block (100 * 100 * 100mm), at 120 ℃ of following forced air drying 8h, be cooled to room temperature then;
(2) in 20L square plastic container, take by weighing 3kg aluminum sulfate respectively and be dissolved in the water of 15L, add lactic acid regulator solution pH value 1.5, be warming up to 60 ℃, under brute force stirs, above-mentioned cellular block is immersed wherein, and strict control pH value, take out after 6 hours,, dry with the clear water flushing;
(3) get 25L square plastic container in addition, add 20% silicon sol solution 15L, under mechanical agitation, add 3X molecular sieve 3kg, after mixing, the modified silica-gel block is slowly immersed wherein, take out liquid purge behind the 30min and dry 2hr,, get molecular sieve and modified silica-gel composite block adsorbent at 150 ℃ of following forced air drying 10hr.
Dispersant is carried out structural characterization and test to the surface texture and the absorption property thereof of the prepared block adsorbent of molecular sieve dispersion effect, the foregoing description.
For comparative effectiveness more directly, with silica gel, the number of patent application of molecular sieve of the present invention and modified silica-gel composite block adsorbent and patent No. ZL02149717.6 development be respectively 200410050867.4 and 200510033982.5 aluminum modified silica, titanium modified silica-gel and equal conditions down the absorption property of the molecular sieve of preparation compare, simultaneously Ludox in the inventive method is compared to the dispersion effect of molecular sieve to waterglass among the dispersion effect of molecular sieve and the patent US4886769.
As seen from Figure 1, Ludox is made dispersant in employing the inventive method, and molecular sieve distributes comparatively even, and dispersion effect is good, and waterglass is made dispersant in the employing US4886769 patent, and molecular sieve easily produces reunites and depositional phenomenon, and dispersion effect is relatively poor.
As can be seen from Figure 2, make dispersant with Ludox, molecular sieve is dispersed in the silica gel comparatively uniformly, and be filled in the space of ceramic fibre, and waterglass is made dispersant in the employing US4886769 patent, and molecular sieve disperses very inhomogeneous, agglomeration occurred, and waterglass produces gas and overflows on the silica gel surface and stay a lot of pores with acid liquid reaction the time, thereby influences distribution and the adhesive strength of molecular sieve on ceramic base material.
As can be seen from Figure 3, adopt the molecular sieve and the modified silica-gel composite block adsorbent of the inventive method preparation, no matter be low humidity condition (RH30%), or high humidity (RH60%), its absorption property all is higher than with the silica gel under the condition, titanium modified silica-gel, aluminum modified silica, molecular sieve.As under the condition of RH60%, the product of embodiment 1 absorption percentage is respectively silica gel, titanium modified silica-gel, molecular sieve 1.448,1.223,1.326 times; Same under the condition of RH30%, the product of embodiment 1 absorption percentage is respectively silica gel, aluminum modified silica, molecular sieve 1.364,1.259,1.168 times.
As Fig. 4, the adsorbent in embodiment 1,2,3 preparations all has absorption property preferably, and is wherein, best with the effect of embodiment 1 (thickness of silica gel 20%).
Fig. 5 compares (embodiment 1,4,5) for the absorption property of gained molecular sieve/modified silica-gel composite block adsorbent under the different molecular sieve addition, and as can be seen, when the molecular sieve addition was 20%, effect was best.
Fig. 6 is the absorption property (embodiment 1,6,7,8) of the molecular sieve under the different metal salt/modified silica-gel composite block adsorbent, as can be seen, adopt the method for complex salt, the composite block adsorbent absorption property that makes than single slaine good (embodiment 1＞embodiment 7＞embodiment 8); And the salt-mixture that adopts titanyl sulfate/aluminum sulfate is than adopting calcium chloride, effective (the embodiment 1＞embodiment 6) of aluminium chloride salt-mixture.
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