CN1089573A

CN1089573A - The producing and manufacturing technique of silica gel and silica gel product thereof

Info

Publication number: CN1089573A
Application number: CN 93110232
Authority: CN
Inventors: 王宁华; 宋彦文
Original assignee: HAIYANG CHEMICAL PLANT QINGDAO
Current assignee: HAIYANG CHEMICAL PLANT QINGDAO
Priority date: 1993-01-04
Filing date: 1993-01-04
Publication date: 1994-07-20
Anticipated expiration: 2013-01-04
Also published as: CN1031749C

Abstract

The invention discloses production technique of a kind of Type B silica gel and products thereof.This process using is rotated hybrid spherical silica gel prilling granulator and is made and adopt a series of aging, acidifyings, washing, activation after the spherical water-setting silica gel, treatment process such as drying, and the mean pore size that makes silica gel is at 0.004-0.007 μ, and specific surface area is at 400-700m ²/ g, mean particle size is at 1-8mm.This silica gel is more suitable in the raw material as fragrance silica gel, and has the advantage that chance water does not burst.

Description

The producing and manufacturing technique of silica gel and silica gel product thereof

The invention discloses a kind of silica gel production technique, especially a kind of producing and manufacturing technique of Type B silica gel and silica gel product thereof, it belongs to technical field of inorganic chemical industry.

Commercially available silica gel by its hole classification, has silochrom and Kiselgel A.This two classes silica gel has can be used as siccative, moisture adsorbent, and sorbent material uses, and what have can be used as various reaction support of the catalyst, and what have can be used as the chromatographic column packing material.These silica gel are because the structure difference of its gel skeleton, the granularity difference, and hole geometry difference, and show difference on the bigger performance.Yet these silica gel all have a shortcoming that the common defective-chance water bursts.This is reason wherein, is exactly the inner skeleton insufficient strength of silica gel, and the aperture of internal void excessive (0.008～0.01 μ) or too small (0.001～0.004 μ) influence frame strength.The Kiselgel A of a kind of chromatographic column with weighting agent arranged, its manufacture method, 62-278113 is disclosed as day disclosure special permission communique: " generate in the silica gel process at silicon sol, its gelation reaction is to carry out in the dispersion agent of organic solvent and nonionogenic tenside formation ".The aftertreatment of its " gelation finish back " be " through filtration, clean, drying finally makes silica gel." in other words, the gelation in dispersant system of its silica gel, i.e. emulsification-gelation-molding, granulating.Wherein the organic solvent of dispersant system and tensio-active agent role are " improve Stir and mix effect " " emulsification is gelation thereafter " this dynamichandling, be unfavorable for that the silica gel skeleton structure becomes to become strong admittedly, so the mean pore size of its silica gel exists: 2～30A ° (0.002～0.003 μ).

The Type B silica gel and the method for manufacturing technology thereof that will provide a kind of skeleton structure strong is provided.This processing method is made spherical water-setting silica gel by the air prilling device, carries out a series of aftertreatment technologys again, makes Type B silica gel.Its frame strength is improved, meet water and do not burst, control its aperture and exist: 0.004～0.007 μ, specific surface area is at 400～700m ²/ g, mean particle size is at 1～8mm, and adsorptive capacity is (60～80) % under relative humidity 90% situation.

Task of the present invention is that following scheme realizes: at first adopt traditional adhesive-preparing technology.Here it is by sodium silicate aqueous solution and dilution heat of sulfuric acid, and through the reaction DL chamber in the hybrid spherical silica gel prilling granulator of CN872128547 number disclosed rotation of patent, reaction generates positive silicic acid.The further polycondensation of this positive silicic acid is also being revolved mixed chamber, and granulation constitutes in nozzle, the spray orifice: granularity is at the water-setting silica gel of 1～12mm.The reaction formula that wherein positive silicic acid polycondensation forms silicon sol is expressed as: (HO) ₃Si OH+H OSi(OH) ₃→ (HO) ₃Si-O-Si(OH) ₃+ H ₂The polymer of O silica sol particle is more poly-bigger, has just formed the hydrogel of silicon.Type B silica gel of the present invention forms in this prilling granulator exactly, and wherein operating pressure is 0.1～0.4MPa, and temperature of reaction is at 10～40 ℃.

Key point of the present invention is: the water-setting silica gel of making (also claiming virgin rubber, hereinafter to be referred as virgin rubber) is carried out a series of aftertreatment technologys, just can make the Type B silica gel of the object of the invention defined.These aftertreatment technologys have:

(1) burin-in process: the many grains of the virgin rubber of granulating and forming are inserted in the basic solution, soaked all former micelles 1～10 hour, control alkali lye pH value 8～12,30～80 ℃ of temperature.This technology pH value and temperature in hand is particularly important.In pH value 8～12 scopes,, make the SiO of virgin rubber inside owing to the effect of OH base ₄The sensible hole of the tridimensional network that tetrahedral structure forms, pore volume is moderate.This is because the OH base can make than the micropore expansion, strengthens Si-O-Si

The hole geometry of key wall makes the three-dimensional netted hole of virgin rubber moderate.

(2) acidification:, insert acidic solution again and soaked 1～8 hour with above-mentioned all former micelles.The compound concentration of this acidic solution should be 1.5～3.5%(W/V).This technology, the first step purpose are the effects that stops the OH base, and the second step purpose is and then uses H ⁺Effect virgin rubber surfaces externally and internally, thus the Na that is adsorbed on its face replaced ⁺Deng metal ion.Because H ⁺The ionic effect makes how much pore texture setting of virgin rubber inside.According to the pH value that former process is handled, temperature, the time, the corresponding processing condition of determining this acidification make this procedure produce the integrated complementary effect, to keep the hole geometry moderate.

(3) washing is handled: with above-mentioned all former micelles, the tap water with clean keeps certain temperature: 20～70 ℃, wash 2～10 times, and washed 3 hours at every turn.This technology utilization warm water is with Na in the virgin rubber ⁺Deng metal ion, H ⁺Ion, SO ⁼ ₄Flushings such as ion are removed, and are washed till till the wash water pH value 7, for next step activating process is laid a solid foundation.

(4) tensio-active agent is handled: with above-mentioned all former micelles, insert content again in 1～8%(W/V) nonionic surfactant solution, immersion treatment 1～12 hour.The key of this technology is, adopts and leaves standstill immersion, makes active agent molecule from outward appearance to inner essence infiltrate virgin rubber hole surfaces externally and internally, thereby can reduce the tension force of virgin rubber pore surface.Like this when next procedure " drying "; because the hot flash evaporation of chance of moisture; and pore surface prestress suddenly increased phenomenon inside and outside virgin rubber can take place, and at this moment can slow down prestressed increase owing to the shielding effect of tensio-active agent, thus the relative rigid matrix structure of protection silica gel.Through activation treatment silica gel, at preparation fragrance silica gel, when inserting silica gel in the spice solution, the unlikely chance water of this silica gel hurriedly bursts, so this silica gel can be used as the raw material of fragrance silica gel.

The selected nonionic surface active agent of the present invention can be: sim alkylphenol Soxylat A 25-7 (TX-9), aliphatic alcohol polyethenoxy silane ether (WA), aliphatic alcohol polyethenoxy thioether, fatty acid amide polyoxyethylene, silk impregnating agent M, the green FB of mill base, poly-ethanol etc.One or more be selected to systems in these nonionogenic tensides are joined the solution of 1-8%.

(5) drying treatment: the former micelle that above-mentioned four step process are handled, in the pallet of packing into, in drying shed, through the oven dry 48 hours down of 80～150 ℃ of hot blasts, after sieving and grading, packaging final prod.

Because virgin rubber is carried out above-mentioned art breading, each treatment process condition is replenished synergy mutually, and make the product of producing and manufacturing technique of the present invention reach: mean pore size is at 0.004～0.007 μ, and average specific surface area is at 400～700m ²/ g, mean particle size is at 1～8mm, and the adsorptive capacity of silica gel is at (60～80) % under relative humidity 90% situation.

Embodiments of the invention are as follows, and protection scope of the present invention is not limited only among the embodiment.

In the experiment, the prepare silicon acid sodium solution reaches 24.5Be ° and makes virgin rubber through nozzle in the CN872128547 patent equipment, its reaction formula with 20% sulphuric acid soln that is mixed with:

Na ₂SiO ₃+ H ₂SO ₄→ Na ₂SO ₄+ H ₂SiO ₃Wherein the operating pressure of granulating equipment is: 0.28～0.3MPa, and temperature of reaction is 25 ± 5 ℃, and it is some to make former micelle, and every lot number is got 10 kilograms of virgin rubbers and is carried out the aftertreatment experiment, concrete experiment condition such as table 1:

Table 1

The processing condition of drying treatment: the virgin rubber of above-mentioned each batch number, shakeout the 30mm thick-layer in baking chamber (case) through sabot, the hot-air seasoning temperature is 120 ℃ ± 5 ℃, dries to silica gel water content≤2%.Analytical test sees Table 2.

Table 2:

Claims

1, a kind of producing and manufacturing technique of Type B silica gel, at first reaction in the hybrid spherical silica gel prilling granulator of rotation generates positive silicic acid by sodium silicate aqueous solution and dilution heat of sulfuric acid for it, and then in, the nozzle indoor in DL step by step polycondensation be a granulated into water-setting silica gel (hereinafter to be referred as: virgin rubber), its this device operating pressure is: 0.1～0.4Mpa, and temperature of reaction exists: 10～40 ℃; Secondly, it is characterized in that: the aftertreatment technology to all former micelles is,

(1) burin-in process: with the many former micelle of granulating and forming, insert in the basic solution, soaked 1～10 hour, control alkali lye pH value 8～12,30～80 ℃ of temperature;

(2) acidification: with above-mentioned all former micelles, insert in the acidic solution again, soaked 1～8 hour, wherein the compound concentration of acidic solution is at 1.5～3.5% (W/V);

(3) washing is handled: wash above-mentioned all former micelles with clean tap water, keep water temperature at 20～70 ℃, wash 2～10 times, washed 3 hours at every turn, be washed till till the pH value 7.

(4) tensio-active agent is handled: with above-mentioned all former micelles, insert content again in the nonionic surface active agent solution of 1～8% (W/V), immersion treatment 1～12 hour;

(5) drying treatment: all former micelle that above-mentioned four steps are handled, through hot wind drying room hot-air seasoning 48 hours, wherein hot blast temperature was at 80～150 ℃.

2, producing and manufacturing technique according to claim 1, it is characterized in that: described tween can be selected for use: the sim alkylphenol Soxylat A 25-7, aliphatic alcohol polyethenoxy silane ether, the aliphatic alcohol polyethenoxy thioether, the fatty acid amide polyoxyethylene, silk impregnating agent M, the green FB of mill base, polyoxyethylene glycol, wherein optional one or more systems are joined solution and are used it.

3, producing and manufacturing technique according to claim 1 and the Type B silica gel product made, it is characterized in that: the mean pore size of this silica gel is at 0.004～0.007 μ, and average specific surface area is at 400～700m ²/ g, under relative humidity 90% situation, its adsorptive capacity is at (70～80) %.