阅读说明：本技术 一种低密度空心玻璃微珠的制备方法 (A kind of preparation method of low-density hollow glass bead ) 是由 许传华 刘亚辉 汪俊 汪光辉 柳雷 彭丽芬 于 2019-10-14 设计创作，主要内容包括：本发明公开了一种低密度空心玻璃微珠的制备方法,将辅料溶液和改性剂溶液均匀分散到泡花碱溶液中制得固含量45～55％的溶液；将制备的溶液输送至离心造粒设备,在入口温度为280-360℃、出口温度100-150℃、离心转速为10000～16500rpm的条件下进行造粒,制得多孔或中空球形颗粒的空心玻璃微珠前驱物,在高温炉中进行玻化制备出低密度空心玻璃微珠。本发明制备的混合溶液中各原料具有分子水平的均匀性,制备的前驱物具有坚硬外壳的多孔或中空球形颗粒,无需发泡剂即可制备出漂浮率高于97％的低密度空心玻璃微珠。本发明采用高温强化工艺,制得的空心玻璃微珠不仅性能好且吸湿性小。本发明原料易得、工艺过程简单且制得的产品储存时间长。(The invention discloses a kind of preparation methods of low-density hollow glass bead, and auxiliary material solution and modifier solution are evenly spread in sodium silicate solution to the solution that solid content 45~55% is made；The solution of preparation is delivered to centrifugal granulating equipment; it is granulated under conditions of inlet temperature is 280-360 DEG C, 100-150 DEG C of outlet temperature, centrifugal rotational speed are 10000~16500rpm; porous or hollow spheroidal particle hollow glass micropearl predecessor is made, vitreous is carried out in high temperature furnace and prepares low-density hollow glass bead.Each raw material has the uniformity of molecular level in mixed solution prepared by the present invention, and the predecessor of preparation has the porous or hollow spheroidal particle of rigid shell, can prepare the low-density hollow glass bead that floatability is higher than 97% without foaming agent.The present invention uses High-Temperature Strengthening technique, and not only performance is good and hygroscopicity is small for hollow glass micropearl obtained.Raw material of the present invention is easy to get, technical process is simple and product storage time obtained is long.)

1. a kind of preparation method of low-density hollow glass bead, it is characterised in that use following technique, step:

1) preparation of colloidal sol: under stirring, auxiliary material solution and modifier solution is evenly spread in sodium silicate solution and made Obtain the solution that solid content is 45~55%；

The auxiliary material solution is magnesium nitrate and boric acid sodium water solution；The modifier solution is polyvinyl alcohol, polyethylene glycol or poly- The aqueous solution that the mass fraction that one or more of acrylic acid mixes in any proportion is 4~9 ‰；The flower bulb alkali soluble Liquid is that solid sodium silicate is dissolved in water waterglass obtained；

2) preparation of hollow glass micropearl predecessor: solution prepared by step 1) is delivered to centrifugal granulating equipment, in entrance temperature Degree is 280-360 DEG C, 100-150 DEG C of outlet temperature, centrifugal rotational speed are granulated under conditions of being 10000~16500rpm, system Obtain porous or hollow spheroidal particle hollow glass micropearl predecessor；

3) preparation of hollow glass micropearl: by the hollow glass micropearl predecessor of step 2) preparation through carrying out vitreous in high temperature furnace, It is 0.12~0.25g/cm that real density, which is made,³, compression strength be 1.5~8MPa, floatability > 97%, partial size are 15~120 μm Low-density hollow glass bead.

2. a kind of preparation method of low-density hollow glass bead as described in claim 1, it is characterised in that: the high temperature furnace It is made of negative pressure system, multicomponent air distribution system, heating system.

3. a kind of preparation method of low-density hollow glass bead as claimed in claim 1 or 2, it is characterised in that: the water Glass Na₂O·nSiO₂N=3.0~3.35.

4. a kind of preparation method of low-density hollow glass bead as claimed in claim 3, it is characterised in that: in step 1) In, the modifier solution accounts for the 2~3.5% of colloidal sol gross mass.

5. a kind of preparation method of low-density hollow glass bead as claimed in claim 4, it is characterised in that: step 1) preparation Colloidal sol in, raw material each component quality sum press 100% timing, each component mass fraction are as follows: sodium silicate 77~89%, magnesium nitrate 0~8%, Boratex 10~17%.

6. a kind of preparation method of low-density hollow glass bead as claimed in claim 5, it is characterised in that: raw material each component Quality sum presses 100% timing, each component mass fraction are as follows: and sodium silicate 78~86%, magnesium nitrate 1~7%, Boratex 11~ 16%.

7. a kind of preparation method of low-density hollow glass bead as claimed in claim 6, it is characterised in that: made in step 2) The surface of standby porous or hollow spheroidal particle hollow glass micropearl predecessor is modified agent cladding, and precursor volume density For 0.5~0.65g/cm³。

Technical field

The invention belongs to inorganic filler preparation technical fields, and in particular to a kind of preparation method of hollow glass micropearl.

Background technique

Hollow glass micropearl is a kind of hollow lightweight micron order spherical particles, low with density, intensity is high, thermally conductive system Count the excellent characteristics such as low, sound insulation, high, the strong, good fluidity of stability of fusing point.Wherein low-density hollow glass bead is in ocean buoyancy Material, thermal insulation material, composite material etc. obtain more extensive purposes, and develop to the material technology of these industries and provide Strong technical support.

Currently, in the world technological precedence and can the industrialization corporate boss for preparing hollow glass micropearl to have U.S. Potter Company, 3M company, Emerson&Cuming company etc., product real density is down to 0.125g/cm3, and industrialization is capable of in the country The minimum 0.20g/cm3 of product real density, and there are at high cost, hygroscopicity is big, easy the disadvantages of agglomerating.Patent CN108191250A A kind of hollow glass micropearl and preparation method thereof is disclosed, and the HGMs real density of preparation is 0.1~0.5g/cm3, but there are technique mistakes Journey is complicated, the disadvantage that energy consumption is high, commercial viability is low.United States Patent (USP) US3796777, US3794503, US3888957 are used Waterglass and ammonium pentaborate are raw material, and through the bulk density of HGM made from multistep high temperature drying < 0.20g/cm3, but there are waterglass It is also easy to produce when being mixed with ammonium pentaborate solution in irreversible gel and production process and discharges ammonia, cause lacking for environmental pollution Point.

Chinese patent CN201610242594.6 discloses a kind of preparation method of hollow glass micropearl, and this method first will The material mixings such as fluorite tailing, dolomite, sieving of milling, and dispersion is mixed with deionized water obtain suspension, and by itself and methanol The heating reaction of the material mixings such as sodium, tetraethyl orthosilicate, then be centrifugated, centrifugation object is placed in sodium hydroxide solution and is impregnated, filtering, Filtrate is washed, dry, calcining obtains class hollow glass micropearl, then uses hydrogen peroxide oxidation and coupling agent modified, mistake respectively Filter is washed, dry, and hollow glass micropearl can be obtained in ball milling.The hollow glass micropearl mechanical property of this method preparation is shown It writes and improves, thermal stability improves 13~15%；And hydrophobicity performance improves, exposure is not easy the moisture absorption in air and hardened, flowing Property is good.But the preparation method of the hollow glass micropearl is only carried out at laboratory, and preparation condition is harsh, is not suitable for big rule Mould industrial application, and hollow glass micropearl density obtained is still higher.

Summary of the invention

The purpose of the present invention is to drawbacks described above of the existing technology, and provide a kind of raw material and be easy to get and cost Low, technical process is simple, hollow glass micropearl hygroscopicity is small, storage time is long high floatability, low-density hollow glass bead Preparation method.The density domination of the low-density hollow glass bead prepared using the method for the present invention is in 0.12~0.25g/cm³ Range, compression strength are 1.5~8MPa, floatability > 97%.

Above-mentioned purpose to realize the present invention, a kind of preparation method of low-density hollow glass bead of the present invention is using following Technique, step:

1) under stirring, auxiliary material solution and modifier solution the preparation of colloidal sol: are evenly spread into sodium silicate solution In be made solid content be 45~55% solution；

The auxiliary material solution is magnesium nitrate and boric acid sodium water solution；The modifier solution is polyvinyl alcohol, polyethylene glycol Or the aqueous solution that the mass fraction that mixes in any proportion of one or more of polyacrylic acid is 4~9 ‰；The flower bulb Aqueous slkali is that solid sodium silicate is dissolved in water waterglass obtained.

2) preparation of hollow glass micropearl predecessor: solution prepared by step 1) is delivered to centrifugal granulating equipment, is being entered Mouth temperature is 280-360 DEG C, outlet temperature is 100-150 DEG C, centrifugal rotational speed is made under conditions of being 10000~16500rpm Grain, is made porous or hollow spheroidal particle hollow glass micropearl predecessor.

3) preparation of hollow glass micropearl: by the hollow glass micropearl predecessor of step 2) preparation through carrying out glass in high temperature furnace Change, the hollow glass micropearl that floatability is higher than 97% is made；

The high temperature furnace is made of negative pressure system, multicomponent air distribution system, heating system.

Preferably, the waterglass Na₂O·nSiO₂, n=3.0~3.35.

Preferably, modifier solution accounts for the 2~3.5% of colloidal sol gross mass.

In order to produce low-density hollow glass bead, preferred each raw material component mass fraction are as follows: sodium silicate 77~89%, Magnesium nitrate 0~8%, Boratex 10~17%；Each component mass fraction is more excellent are as follows: sodium silicate 78~86%, magnesium nitrate 1~7%, Boratex 11~16%.

According to above scheme, the hollow glass micropearl real density of preparation is 0.12~0.25g/cm³, compression strength 1.5 ~8MPa, floatability > 97%, partial size are 15~120 μm.

A kind of preparation method of low-density hollow glass bead of the present invention after the above technical solution is adopted, has beneficial below Effect:

(1) raw material is easy to get, and is not necessarily to foaming agent, former by the gas foaming that the hard spherical shell of forerunner's composition granule is coated Expect at low cost.

(2) uniformity of each raw material with molecular level in the solution prepared, avoids HGMs glass spherical shell split-phase defect Generation.

(3) modifying agent forms film coated on predecessor surface, before raising during centrifugal granulating in the solution prepared Drive object mobility and dispersibility, thus reduce fuse during interfering with each other between particle, improving HGMs, (hollow glass is micro- Pearl) balling ratio.

(4) HGMs volatilizees, remaining alkali metal is located at borosilicate skeleton through high temperature vitreous in hot stage partial alkaline-metal In gap, difficult, reduction HGMs hygroscopicity is precipitated in alkali metal, while the HGMs intensity of sufficiently vitreous is improved.

Specific embodiment

To further describe the present invention, below with reference to embodiment, to a kind of system of low-density hollow glass bead of the present invention Preparation Method is described further.But the invention is not limited to embodiments.