WO2021073060A1 - 一种高漂浮率的空心玻璃微珠的制备方法 - Google Patents

一种高漂浮率的空心玻璃微珠的制备方法 Download PDF

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WO2021073060A1
WO2021073060A1 PCT/CN2020/084454 CN2020084454W WO2021073060A1 WO 2021073060 A1 WO2021073060 A1 WO 2021073060A1 CN 2020084454 W CN2020084454 W CN 2020084454W WO 2021073060 A1 WO2021073060 A1 WO 2021073060A1
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Prior art keywords
hollow glass
slurry
glass beads
mass
sodium
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PCT/CN2020/084454
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English (en)
French (fr)
Inventor
许传华
刘亚辉
汪俊
汪光辉
柳雷
彭丽芬
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中钢集团马鞍山矿山研究总院股份有限公司
中钢集团马鞍山矿院新材料科技有限公司
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Priority to DE112020000050.8T priority Critical patent/DE112020000050T5/de
Publication of WO2021073060A1 publication Critical patent/WO2021073060A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C03C11/002—Hollow glass particles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/107—Forming hollow beads
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Definitions

  • the invention relates to inorganic fillers, in particular to a hollow glass microsphere, which can be widely used in the fields of petroleum, chemical industry, military industry, shipbuilding, automobile, aerospace, building materials, etc., and is especially suitable for coatings, glass fiber reinforced plastics, oil and gas field mining, and epoxy/ Unsaturated resins, nitrile, phenolic, acrylic and other coatings, as well as inks, adhesives, sealants, emulsion explosives and other products.
  • Hollow glass beads are hollow micron-sized spherical particles, which have excellent characteristics such as low density, high strength, low thermal conductivity, sound insulation, high melting point, strong stability, and good fluidity. It is precisely because of this series of advantages. Make it an excellent modified material, endow the substrate with multiple functions, so it is widely used in petroleum, military, building materials, automobiles, plastics, paint, explosives and other industries.
  • the industrialized hollow glass microbead preparation technologies mainly include soft chemical method, solid phase powder method and liquid phase atomization method.
  • the production method of 3M Company in the United States is a solid phase powder method, as described in patents US4391646, US3365315, WO2017/040900 A1, the hollow glass beads prepared have high performance and good chemical stability, but the process is complex, the floating rate is low, and energy consumption High; PQ’s production method is a liquid phase atomization method, as described in patents US3794503 and US3796777.
  • the process is simple, low energy consumption, high floating rate, but the raw materials are limited, and the hollow glass beads prepared are low in strength and easy Agglomeration; the properties of hollow glass beads prepared by soft chemical method are between the solid phase powder method and the soft chemical method, and the process is simple, but there are disadvantages such as excessive fuel cost and easy agglomeration.
  • HGMs hollow glass microspheres
  • relevant domestic enterprises and research institutions have made improvements in process or formulation in terms of surface modification.
  • Chinese Patent CN 101704632 B (ZL 200910185799.5) discloses a method for preparing high-strength and low-density hollow glass beads.
  • the raw material composition of the hollow glass beads is SiO. 2 70 ⁇ 80%, Na 2 O 8 ⁇ 12%, CaO 5 ⁇ 9%, B 2 O 3 2 ⁇ 6%, SO 3 0.2 ⁇ 0.5%, K 2 O or Li 2 O 0 ⁇ 5%, ZnO or BaO 0 ⁇ 5%, Al 2 O 3 0 ⁇ 3%.
  • this preparation method uses SO 3 as a foaming agent, which is harmful to the environment and has safety risks.
  • the hollow glass microspheres prepared by this method have a single product, the crushing strength of the hollow microspheres is 16 to 23 MPa, and the application range is narrow. .
  • the purpose of the present invention is to address the above-mentioned defects in the prior art, and provide a high-floating material with easily available raw materials, high spheroidization rate of hollow glass beads, simple process, low energy consumption, low production cost and wide product application range.
  • the method of preparing hollow glass microspheres with high efficiency By optimizing the formulation of raw materials, the preparation of stable dispersion slurry, the control of the process parameters of the atomized granulation equipment, the application of high-temperature negative pressure sintering and low-temperature circulating air strengthening technology, the floating rate and strength of the hollow glass beads are improved, and the particle size The distribution is controlled.
  • a method for preparing hollow glass beads with a high floating rate of the present invention adopts the following processes and steps:
  • Preparation of slurry accurately weigh the components of the basic raw materials, stable dispersant and surfactant, and use a flow meter to measure a certain quality of water; combine the components of the basic raw materials, stabilized dispersant, surfactant and water After mixing for 15-20 minutes in the dispersion tank, it is transported to the ball mill by the feed pump to prepare a slurry with a solid content of 55-65%, with a particle size of ⁇ 10 ⁇ m;
  • the basic raw material is a mixture of quartz, borax, calcium carbonate, sodium carbonate, sodium sulfate, and sodium phosphate.
  • the content of each component is: 60.30-61.15% of quartz, borax 14.00 ⁇ 14.90%, calcium carbonate 19.15 ⁇ 20.80%, sodium carbonate 3.40 ⁇ 3.80%, sodium sulfate 0.22 ⁇ 0.81%, sodium phosphate 0.41 ⁇ 1.25%;
  • the stable dispersant is sodium polyacrylate, sodium tripolyphosphate, poly
  • the surfactant is a fluorocarbon surfactant or a silicone surfactant; the stable dispersant accounts for 0.1 to 0.5% of the mass of the slurry, Said surfactant accounts for 0.05-0.2% of the mass of the slurry;
  • the mixed slurry prepared in step 1) is transported to the spray granulation equipment through a feeding pump, and carried out under the conditions of an inlet temperature of 280-425°C, an outlet temperature of 100-155°C, and a centrifugal speed of 10000-16500 rpm Spray granulation, the powder collected by the cyclone is a high-fluidity solid ball-the precursor of hollow glass beads;
  • step 2) the droplets atomized by the slurry have a low probability of collision and agglomeration during the drying process.
  • the hollow glass microbead precursor is made to flow. Solid spheres with good properties and narrow particle size distribution, with a particle size of 1-100 ⁇ m and a moisture content of 3 to 5%.
  • the precursor of the hollow glass microbeads prepared in step 2) is transported to the sintering equipment through the powder feeding equipment, and the sintering is completed under the synergistic effect of the negative pressure system, the multi-group distribution gas system, and the heating system
  • the vitrification process is then transported to the cooling tower by air flow, and the strengthening process is completed by circulating air at room temperature, and the hollow glass microbead products are collected through the collection equipment;
  • the method of the present invention adopts room temperature air for quenching, effectively prevents phase separation and crystallization of the glass, and improves the strength of hollow glass beads; the present invention realizes the control of the mixing ratio of each gas through the high-temperature negative pressure vitrification combined with the multi-group distribution gas system.
  • the flame temperature, height and thermal conductivity are controlled to adjust the internal and external pressure of the spherical shell, as well as the surface tension and viscosity of the glass liquid phase, thereby controlling the expansion rate, sphericity and uniformity of the spherical shell, reducing the production of solid balls and preparing floats.
  • Hollow glass beads with a rate of >96.5% and a high surface finish.
  • step 3) Surface modification: the hollow glass microbeads collected in step 3) and the surface modifier are passed through a dry continuous powder surface modification equipment to complete the coating process to obtain surface modified hollow glass microbeads;
  • Surface modifiers refer to modifiers that can form chemical bonds, hydrogen bonds or physical adsorption with the silanol groups on the glass surface.
  • step 4 if the surface modifier used is liquid, the modification temperature is controlled between 100 and 120°C, and the rotating speed of the dry continuous powder surface modification equipment is 1450 rpm to 1550 rpm; if the surface is used If the modifier is a solid powder, the heating system is turned off and the modification is carried out at room temperature. The rotating speed of the dry continuous powder surface modification equipment is 1450-1550 rpm.
  • the surface modifiers are preferably silane coupling agents, oligomers, and active nano-level powders.
  • the addition amount of the liquid surface modifier is 0.5 to 1.5% of the mass of the hollow glass microspheres, and the addition amount of the solid surface modifier is 1 to 3% of the mass of the hollow glass microspheres.
  • the basic raw material formula used is preferably: quartz 60.60 ⁇ 61.10%, borax 14.20 ⁇ 14.50%, calcium carbonate 20.30 ⁇ 20.75%, sodium carbonate 3.45 to 3.80%, sodium sulfate 0.24 to 0.26%, sodium phosphate 0.42 to 0.48%; the stable dispersant accounts for 0.26 to 0.35% of the mass of the slurry, and the surfactant accounts for 0.08 to 0.12% of the mass of the slurry
  • the process parameters of the spray granulation equipment are: centrifugal speed 15700-16300rpm, inlet temperature 285-295°C, outlet temperature 105-115°C; the true density of the prepared hollow glass beads is 0.45-0.55g /cm 3 , compressive strength>115Ma, floating rate>96.5%.
  • the basic raw material formula used is preferably: quartz 60.70-61.15%, borax 14.10-14.50%, calcium carbonate 19.85-20.35%, carbonic acid Sodium 3.45 ⁇ 3.80%, sodium sulfate 0.36 ⁇ 0.53%, sodium phosphate 0.60 ⁇ 0.78%; the stabilizing dispersant accounts for 0.18 ⁇ 0.30% of the mass of the slurry, and the said surfactant accounts for 0.06 ⁇ 0.16 of the mass of the slurry %;
  • the process parameters of the spray granulation equipment are: centrifugal speed 13000-14800rpm, inlet temperature 330-375°C, outlet temperature 135-150°C; the true density of the prepared hollow glass beads is 0.30-0.41 g/cm 3 , compressive strength 27 ⁇ 55Ma, floating rate>98.0%.
  • the market requires hollow glass beads with a compressive strength of only a few MPa, such as emulsion explosives and paint industries.
  • the basic raw material formula used is preferably 60.35-60.60% quartz and 14.45- borax. 14.75%, calcium carbonate 19.15-19.50%, sodium carbonate 3.45-3.80%, sodium sulfate 0.75-0.81%, sodium phosphate 1.05-1.25%; the stabilizing dispersant accounts for 0.28-0.32% of the mass of the slurry.
  • the spray granulation equipment process parameters are: centrifugal speed 9500-10500rpm, inlet temperature 400-425°C, outlet temperature 145-155°C; prepared
  • the true density of the hollow glass beads is 0.11 ⁇ 0.13g/cm 3 , the compressive strength>3Ma, and the floating rate>97.5%.
  • the prepared hollow glass beads have a true density of 0.11 to 0.55 g/cm 3 , a compressive strength of 3 to 180 MPa, a floating rate of >96.5%, and a particle size of 2 to 150 ⁇ m.
  • the present invention has the following beneficial effects:
  • the raw materials are easily available and are not limited by solubility.
  • Stable dispersion slurry with high solid content prepared by adding stable dispersant and surfactant, while improving the matching degree of slurry surface tension and viscosity with the process parameters of spray granulation equipment, not only reduces the energy consumption of granulation, but also Moreover, the prepared solid spherical precursor has uniform composition, good fluidity, narrow and controllable particle size distribution.
  • the surface modifier is not limited by the physical state, has wide selectivity, does not need to be dried, simplifies the process, reduces energy consumption, and at the same time broadens the product application range.
  • the method for preparing a hollow glass microbead with a high floating rate of the present invention will be further described below in conjunction with examples.
  • the present invention is not limited to the embodiment.
  • the slurry is transported to the spray granulation equipment by the feeding pump, and the spray granulation is carried out under the conditions of inlet temperature of 280 ⁇ 420°C, outlet temperature of 100 ⁇ 150°C and centrifugal rotation speed of 10000 ⁇ 16000rpm.
  • the powder collected by the cyclone is High-fluidity solid ball, the particle size of the solid ball is 1-100 ⁇ m, and the water content is 3 to 5%.
  • the precursor particles are transported to the sintering equipment through the powder feeding equipment, and the sintering process is completed under the synergy of the negative pressure system, the multi-group distribution air system, and the heating system, and then transported to the cooling tower through the airflow to complete the low-temperature circulating air. Strengthen the process and collect hollow glass microbead products through collection equipment.
  • the surface modifier is selected, and the surface modified hollow glass microspheres are prepared by the dry continuous powder surface modification equipment.
  • the modification temperature is set to 100-120°C and the rotation speed is 1500 rpm; when the surface modifier is solid, the heating system is turned off and the modification is performed at room temperature, and the rotation speed is set to 1500 rpm.
  • Example 1 to 4 The preparation processes of Examples 1 to 4 are the same, and the parameters in the preparation process are shown in Table 1.
  • the upper and lower limit values and interval values of the additives involved in the present invention can all realize the present invention, and the upper and lower limit values and interval values of the process parameters of the present invention (such as spray granulation process parameters, modified process parameters, etc.) can be realized.
  • the embodiments of the present invention are not listed here.
  • Table 1 The preparation process parameters of Examples 1 to 4 and the properties of the hollow glass beads prepared
  • Strength refers to the pressure applied when the survival rate of hollow glass beads is 80%.

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Abstract

本发明公开了一种高漂浮率的空心玻璃微珠的制备方法，其生产工艺、步骤为：1)料浆的制备：准确称量基本原料各组份、稳定分散剂和表面活性剂；基本原料各组份为石英、硼砂、碳酸钙、碳酸钠、硫酸钠、磷酸钠；2)前驱物的制备；3)空心玻璃微珠的制备；4)表面改性。本发明方法制备的稳定分散料浆固相含量高且表面张力和粘度低，不仅显著降低了喷雾造粒能耗，而且制备的前驱物粒径跨度小且成分均匀，结合高温负压玻化工艺使空心玻璃微珠漂浮率高于96.5％且表面光洁度高，并采用低温循环风强化空心玻璃微珠。本发明原材料易得、空心玻璃微珠成球率高、工艺过程简单，能耗低、生产成本低且产品应用范围广。

Description

一种高漂浮率的空心玻璃微珠的制备方法 技术领域
本发明涉及无机填料，特别涉及一种空心玻璃微珠，可广泛应用于石油、化工、军工、造船、汽车、航天航空、建材等领域，尤其适用于涂料、玻璃钢、油气田开采，以及环氧/不饱和树脂，腈类、酚醛、丙烯酸等涂料，以及油墨、胶粘剂、密封胶、乳化***等产品。
背景技术
空心玻璃微珠是一种中空的微米级球型颗粒，其具有密度低、强度高、导热系数低、隔音、熔点高、稳定性强、流动性好等优异特性，正因这一系列的优点使其成为一种优良的改性材料，赋予基材多种功能，因此被广泛应用于石油、军工、建材、汽车、塑料、油漆、***等行业。
目前，已实现产业化的空心玻璃微珠制备技术主要有软化学法、固相粉末法和液相雾化法。美国3M公司的生产方法为固相粉末法，如专利US4391646、US3365315、WO2017/040900 A1中所述，制备的空心玻璃微珠性能高且化学稳定性好，但工艺复杂、漂浮率低、能耗高；PQ公司的生产方法为液相雾化法，如专利US3794503、US3796777中所述，工艺简单、能耗低、漂浮率高，但原料受限，且制备的空心玻璃微珠强度低、易结块；软化学法制备的空心玻璃微珠性能介于固相粉末法和软化学法之间，工艺简单，但存在燃料所占成本比例过大、易结块等缺点。国内相关企业及研究机构，为提高空心玻璃微珠(HGMs)强度、漂浮率，在表面改性等方面进行了工艺或配方的改进，但仍存在原料成本高、工艺复杂、粒径分布宽、强度低等缺点。
为制备高强度低密度的空心玻璃微珠，中国专利CN 101704632 B(ZL 200910185799.5)公开了一种高强度低密度空心玻璃微珠的制 备方法，该空心玻璃微珠重量配比的原料组成：SiO 2 70～80％，Na 2O 8～12％，CaO 5～9％，B 2O 3 2～6％，SO 3 0.2～0.5％，K 2O或Li 2O 0～5％，ZnO或BaO 0～5％，Al 2O 3 0～3％。但该制备方法采用SO 3作为发泡剂，对环境的危害大，并具有安全风险，而且该方法制备出的空心玻璃微珠产品单一，空心微珠压碎强度在16～23MPa，应用范围窄。
发明内容
本发明的目的就是针对现有技术存在的上述缺陷，而提供一种原材料易得、空心玻璃微珠成球率高、工艺过程简单，能耗低、生产成本低且产品应用范围广的高漂浮率的空心玻璃微珠的制备方法。通过优化原料配方、稳定分散料浆的制备、雾化造粒设备工艺参数的控制、高温负压烧结和低温循环风强化技术的应用，使空心玻璃微珠的漂浮率和强度得到提高，粒径分布得到控制。
为实现本发明的上述目的，本发明一种高漂浮率的空心玻璃微珠的制备方法采用以下工艺、步骤：
1)料浆的制备：准确称量基本原料各组份、稳定分散剂和表面活性剂，并采用流量计计量一定质量的水；将基本原料各组份、稳定分散剂、表面活性剂和水通过分散罐混合15～20分钟后，经送料泵输送至球磨机，制得固相含量为55～65％的料浆，粒径≤10μm；
所述的基本原料为石英、硼砂、碳酸钙、碳酸钠、硫酸钠、磷酸钠的混合物，基本原料各组份质量之和按100％计算时各组份含量为：石英60.30～61.15％，硼砂14.00～14.90％，碳酸钙19.15～20.80％，碳酸钠3.40～3.80％，硫酸钠0.22～0.81％，磷酸钠0.41～1.25％；所述的稳定分散剂为聚丙烯酸钠、三聚磷酸钠、聚乙二醇中的一种或几种按任意比例混合，所述的表面活性剂为氟碳表面活性剂或有机硅表面活性剂；所述的稳定分散剂占料浆质量的0.1～0.5％，所述的表面活性剂占料浆质量的0.05～0.2％；
2)前驱物的制备：将步骤1)制备的混合料浆经送料泵输送至 喷雾造粒设备，在入口温度为280～425℃、出口温度100～155℃、离心转速10000～16500rpm条件下进行喷雾造粒，旋风收集的粉体为高流动性实心球——空心玻璃微珠前驱物；
在步骤2)中，料浆雾化成的液滴在干燥过程中再碰撞、团聚的概率低，结合稳定分散剂和表面活性剂对料浆性能的调控，制得空心玻璃微珠前驱物为流动性好且粒径分布窄的实心球，粒径为1～100μm、含水率在3～5％之间。
3)空心玻璃微珠的制备：将步骤2)制备的空心玻璃微珠前驱物经送粉设备输送至烧结设备中，在负压***、多组分配气***、加热***的协同作用下完成烧结玻化过程，然后经气流输送至冷却塔中经室温循环风完成强化过程，并通过收集设备收集空心玻璃微珠产品；
本发明方法采用室温空气进行骤冷，有效防止玻璃分相和析晶，提高空心玻璃微珠强度；本发明通过高温负压玻化，结合多组分配气***对各气体混合比例的调控，实现火焰温度、高度以及热传导系数的控制，从而调节球壳内外压强，以及玻璃液相表面张力和粘度，进而控制球壳膨胀速率、球形度和球壳均匀性，减少实心球的产生，制备出漂浮率>96.5％且表面光洁度高的空心玻璃微珠。
4)表面改性：将步骤3)收集的空心玻璃微珠产品与表面改性剂通过干法连续式粉体表面改性设备完成包覆过程，制得表面改性空心玻璃微珠；所述表面改性剂是指能与玻璃表面硅羟基形成化学键合、氢键或物理吸附作用的改性剂。
在步骤4)中，如果采用的表面改性剂为液体，则改性温度控制在100～120℃之间，干法连续式粉体表面改性设备的转速为1450rpm～1550rpm；如果采用的表面改性剂为固体粉末，则关闭加热***，在室温下进行改性，干法连续式粉体表面改性设备转速为1450～1550rpm。
表面改性剂优选硅烷偶联剂、低聚物、活性纳米级粉体。液体表面改性剂添加量为空心玻璃微珠质量的0.5～1.5％，固体表面改性剂添加量为空心玻璃微珠质量的1～3％。
为了生产抗压强度大于115MPa(最高可达180MPa)的高性能空心玻璃微珠，采用的基本原料配方优选为：石英60.60～61.10％，硼砂14.20～14.50％，碳酸钙20.30～20.75％，碳酸钠3.45～3.80％，硫酸钠0.24～0.26％，磷酸钠0.42～0.48％；所述的稳定分散剂占料浆质量的0.26～0.35％，所述的表面活性剂占料浆质量的0.08～0.12％；在步骤2)中，喷雾造粒设备工艺参数为：离心转速15700～16300rpm、入口温度285～295℃、出口温度105～115℃；制备出的空心玻璃微珠的真密度在0.45～0.55g/cm 3，抗压强度>115Ma，漂浮率>96.5％。
为了生产抗压强度在25～70MPa之间的中高抗压强度的空心玻璃微珠，采用的基本原料配方优选为：石英60.70～61.15％，硼砂14.10～14.50％，碳酸钙19.85～20.35％，碳酸钠3.45～3.80％，硫酸钠0.36～0.53％，磷酸钠0.60～0.78％；所述的稳定分散剂占料浆质量的0.18～0.30％，所述的表面活性剂占料浆质量的0.06～0.16％；在步骤2)中，喷雾造粒设备工艺参数为：离心转速13000～14800rpm、入口温度330～375℃、出口温度135～150℃；制备出的空心玻璃微珠的真密度在0.30～0.41g/cm 3，抗压强度27～55Ma，漂浮率>98.0％。
在有些情况下，市场需要抗压强度仅为几个MPa的空心玻璃微珠，例如乳化***、油漆行业，为了降低生产成本，采用的基本原料配方优选为：石英60.35～60.60％，硼砂14.45～14.75％，碳酸钙19.15～19.50％，碳酸钠3.45～3.80％，硫酸钠0.75～0.81％，磷酸钠1.05～1.25％；所述的稳定分散剂占料浆质量的0.28～0.32％，所述的表面活性剂占料浆质量的0.16～0.2％；在步骤2)中，喷雾造粒设备工艺参数为：离心转速9500～10500rpm、入口温度400～425℃、出口温度145～155℃；制备出的空心玻璃微珠的真密度在0.11～0.13g/cm 3，抗 压强度>3Ma，漂浮率>97.5％。
根据上述方案，制备的空心玻璃微珠真密度为0.11～0.55g/cm 3，抗压强度为3～180MPa，漂浮率>96.5％，粒径为2～150μm。
本发明采用以上技术方案后，具有以下有益效果：
(1)原材料易获得，不受溶解度限制。
(2)通过添加稳定分散剂和表面活性剂制备的高固相含量稳定分散料浆，同时提高了料浆表面张力、粘度与喷雾造粒设备工艺参数的匹配度，不仅降低造粒能耗，而且制备的实心球型前驱物成分均匀、流动性好、粒径分布窄且可控。
(3)采用高温负压玻化工艺与多组分配气工艺，实现烧结过程三要素——温度、气氛、压力的精准控制，从而实现对球壳内外压差、玻璃液相表面张力和粘度的调节，进而控制球壳膨胀速率、球形度和球壳均匀性，减少实心球的产生，制备的空心玻璃微珠成球率≥96.5％且性能高。
(4)采用低温循环风强化工艺，防止玻璃分相和析晶，进一步提高了空心玻璃微珠强度。
(5)采用干法表面改性工艺，表面改性剂不受物理状态的限制，选择性广，无需进行干燥，简化工艺过程，降低能耗，同时，拓宽了产品应用范围。
具体实施方式
为进一步描述本发明，下面结合实施例，对本发明一种高漂浮率的空心玻璃微珠的制备方法做进一步说明。但本发明并不局限于实施例。
本发明一种高漂浮率的空心玻璃微珠的制备方法具体实施过程如下：
(1)准确称取原料、表面活性剂和稳定分散剂，并采用流量计计量一定质量的水，通过分散罐混合15～20分钟后，经送料泵输送至 球磨机，制得固相含量为55～65％的料浆。
(2)将料浆经送料泵输送至喷雾造粒设备，在入口温度为280～420℃、出口温度100～150℃、离心转速10000～16000rpm条件下进行喷雾造粒，旋风收集的粉体为高流动性实心球，实心球粒径为1～100μm、含水率为3～5％。
(3)前驱物颗粒经送粉设备输送至烧结设备中，在负压***、多组分配气***、加热***的协同作用下完成烧结过程，然后经气流输送至冷却塔中经低温循环风完成强化过程，并通过收集设备收集空心玻璃微珠产品。
(4)根据应用，选择表面改性剂，经干法连续式粉体表面改性设备制备表面改性空心玻璃微珠。表面改性剂为液体时，设定改性温度为100～120℃、转速为1500rpm；表面改性剂为固体时，关闭加热***，在室温下进行改性，设定转速为1500rpm。
实施例1～4的制备过程相同，制备过程中的参数见表1。本发明涉及的各添加剂的上下限取值、区间值均能实现本发明，本发明的工艺参数(如喷雾造粒工艺参数、改性工艺参数等)的上下限取值、区间值均能实现本发明，在此不一一列举实施例。
表1 实施例1～4制备过程参数及制备出的空心玻璃微珠性能
Figure PCTCN2020084454-appb-000001
Figure PCTCN2020084454-appb-000002
注：强度是指空心玻璃微珠存活率为80％时施加的压力。

Claims (6)

  1. 一种高漂浮率的空心玻璃微珠的制备方法，其特征在于采用以下工艺、步骤制备出在水中的漂浮率>96.5％的空心玻璃微珠：
    1)料浆的制备：准确称量基本原料各组份、稳定分散剂和表面活性剂，并采用流量计计量一定质量的水；将基本原料各组份、稳定分散剂、表面活性剂和水通过分散罐混合15～20分钟后，经送料泵输送至球磨机，制得固相含量为55～65％的料浆；
    所述的基本原料为石英、硼砂、碳酸钙、碳酸钠、硫酸钠、磷酸钠的混合物，基本原料各组份质量之和按100％计算时各组份含量为：石英60.30～61.15％，硼砂14.00～14.90％，碳酸钙19.15～20.80％，碳酸钠3.40～3.80％，硫酸钠0.22～0.81％，磷酸钠0.41～1.25％；所述的稳定分散剂为聚丙烯酸钠、三聚磷酸钠、聚乙二醇中的一种或几种按任意比例混合，所述的表面活性剂为氟碳表面活性剂或有机硅表面活性剂；所述的稳定分散剂占料浆质量的0.1～0.5％，所述的表面活性剂占料浆质量的0.05～0.2％；
    2)前驱物的制备：将步骤1)制备的混合料浆经送料泵输送至喷雾造粒设备，在入口温度为280～425℃、出口温度100～155℃、离心转速10000～16500rpm条件下进行喷雾造粒，旋风收集的粉体为高流动性实心球——空心玻璃微珠前驱物；
    3)空心玻璃微珠的制备：将步骤2)制备的空心玻璃微珠前驱物经送粉设备输送至烧结设备中，在负压***、多组分配气***、加热***的协同作用下完成烧结过程，然后经气流输送至冷却塔中经室温循环风完成强化过程，并通过收集设备收集空心玻璃微珠产品；
    4)表面改性：将步骤3)收集的空心玻璃微珠产品与表面改性剂通过干法连续式粉体表面改性设备完成包覆过程，制得表面改性空心玻璃微珠；所述表面改性剂是指能与玻璃表面硅羟基形成化学键合、氢键或物理吸附作用的改性剂。
  2. 如权利要求1所述的一种高漂浮率的空心玻璃微珠的制备方法，其特征在于：在步骤4)中采用的表面改性剂为液体，改性温度为100～120℃，干法连续式粉体表面改性设备的转速为1450rpm～1550rpm。
  3. 如权利要求1所述的一种高漂浮率的空心玻璃微珠的制备方法，其特征在于：在步骤4)中采用的表面改性剂为固体粉末，关闭加热***，在室温下进行改性，干法连续式粉体表面改性设备转速为1450～1550rpm。
  4. 如权利要求1、2或3所述的一种高漂浮率的空心玻璃微珠的制备方法，其特征在于：基本原料各组份质量之和按100％计算时各组份含量为：石英60.60～61.10％，硼砂14.20～14.50％，碳酸钙20.30～20.75％，碳酸钠3.45～3.80％，硫酸钠0.24～0.26％，磷酸钠0.42～0.48％；所述的稳定分散剂占料浆质量的0.26～0.35％，所述的表面活性剂占料浆质量的0.08～0.12％；在步骤2)中，喷雾造粒设备工艺参数为：离心转速15700～16300rpm、入口温度285～295℃、出口温度105～115℃；制备出的空心玻璃微珠的真密度在0.45～0.55g/cm 3，抗压强度>115Ma，漂浮率>96.5％。
  5. 如权利要求1、2或3所述的一种高漂浮率的空心玻璃微珠的制备方法，其特征在于：基本原料各组份质量之和按100％计算时各组份含量为：石英60.70～61.15％，硼砂14.10～14.50％，碳酸钙19.85～20.35％，碳酸钠3.45～3.80％，硫酸钠0.36～0.53％，磷酸钠0.60～0.78％；所述的稳定分散剂占料浆质量的0.18～0.30％，所述的表面活性剂占料浆质量的0.06～0.16％；在步骤2)中，喷雾造粒设备工艺参数为：离心转速13000～14800rpm、入口温度330～375℃、出口温度135～150℃；制备出的空心玻璃微珠的真密度在0.30～0.41g/cm 3，抗压强度27～55Ma，漂浮率>98.0％。
  6. 如权利要求1、2或3所述的一种高漂浮率的空心玻璃微珠的 制备方法，其特征在于：基本原料各组份质量之和按100％计算时各组份含量为：石英60.35～60.60％，硼砂14.45～14.75％，碳酸钙19.15～19.50％，碳酸钠3.45～3.80％，硫酸钠0.75～0.81％，磷酸钠1.05～1.25％；所述的稳定分散剂占料浆质量的0.28～0.32％，所述的表面活性剂占料浆质量的0.16～0.2％；在步骤2)中，喷雾造粒设备工艺参数为：离心转速9500～10500rpm、入口温度400～425℃、出口温度145～155℃；制备出的空心玻璃微珠的真密度在0.11～0.13g/cm 3，抗压强度>3Ma，漂浮率>97.5％。
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