CN1123772A - Manufacture of hollow glass micro-ball - Google Patents
Manufacture of hollow glass micro-ball Download PDFInfo
- Publication number
- CN1123772A CN1123772A CN 94114205 CN94114205A CN1123772A CN 1123772 A CN1123772 A CN 1123772A CN 94114205 CN94114205 CN 94114205 CN 94114205 A CN94114205 A CN 94114205A CN 1123772 A CN1123772 A CN 1123772A
- Authority
- CN
- China
- Prior art keywords
- hollow glass
- solution
- glass microspheres
- producing hollow
- spray drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The process for preparing hollow glass microballoons used as filler of unsaturated polyester, resin, paint, adhesive, sealing agent, detergent and putty with excellent performance, good chemical stability, high strength and low oil absorption includes preparing solution and spray drying, and features use of the secondary air atomizing nozzle for spray drying to simplify technology and lower cost. The obtained microballoons has water content of less than 2.0%, fineness of under 50 micrometers, unit weight of 0.1-0.2g/cu.cm and breakage rate of less than 3%.
Description
The invention relates to a method for manufacturing hollow glass microspheres, belonging to a method for spraying and solidifying liquid raw materials into beads by utilizing chemical and physical methods.
The hollow glass microsphere is an ideal filler for paint, adhesive, sealant, detergent, putty and synthetic resin, especially unsaturated polyester. Therefore, many departments are engaged in the research of the manufacturing method of the hollow glass microsphere at home and abroad, and the research direction is focused on reducing the cost, improving the performance and simplifying the process. In british patent 1426801, a method for manufacturing hollow glass microspheres is disclosed, comprising the steps of:
a. preparing a first solution, namely a sodium silicate solution;
b. preparing a second solution, namely an ammonium borate solution;
c. mixing the first solution and the second solution;
d. taking out the mixed solution;
e. spray drying with centrifugal atomizer to obtain hollow glass microsphere with water content below 25%;
f. secondly drying the microspheres subjected to spray drying at the temperature of 70-400 ℃ until the moisture content is below 7%;
g. and collecting the hollow microspheres.
The manufacturing method has the following defects:
a. secondary drying is needed, the process is complex, the period is prolonged, and the energy consumption is increased;
b. centrifugal atomization is carried out, the particle size of the microspheres is large and uneven, the balling rate is low, and the oil absorption is large; the strength of the spherical membrane is also affected;
c. the cost is high.
The invention aims to avoid the defects in the prior art and provides an ideal manufacturing method of hollow glass microspheres which have the advantages of simple process, lower cost, secondary air atomization, primary balling and drying, and good chemical stability, low oil absorption, fine and uniform granularity, high strength and good water resistance.
The invention also aims to provide a simple microsphere surface treatment method, so that the water resistance of the microsphere is improved; in addition, apreparation method of the ammonium pentaborate solution with low price is also provided, so that the production cost is further reduced, and the market competitiveness of the product is improved.
The object of the present invention can be achieved by the following measures;
the method for manufacturing the hollow glass microspheres comprises the following steps;
a. preparation of an aqueous ammonium polyborate solution A: adding the measured ammonium polyborate and water into the solution A preparation tank 1, heating and stirring to dissolve the ammonium polyborate and water for later use;
b. preparing an alkali metal silicate aqueous solution B: adding the raw material of the aqueous solution of the salt of the inerter acid into a proportioning tank 3 according to the preset proportioning proportion for mixing;
c. adding the solution A into the solution B through a pump 2, adding a waterproof agent, stirring uniformly, pumping the mixed solution into a mixed solution storage tank 17 through a pump 4, and preparing for spray drying;
d. spray drying: sequentially starting an air compressor 15, an induced draft fan 14 and a hot air blower 6, and adjusting and controlling the air compressor, the induced draft fan and the hot air blower to be in a use state; then the inserting plate 7 is opened, the materials in the mixed liquid storage tank 17 enter the spray drying tower 8 through the secondary air atomizing nozzle 9 according to a certain flow rate, and are formed into balls in the spray drying tower 8 from bottom to top along with hot air entering from the bottom of the tower for drying, the dried microspheres pass through the primary separator 10 and the secondary separator 12 in sequence under the suction of the induced draft fan 14, almost all the microspheres are separated and collected, and tail gas is exhausted. The product hollow glass microspheres are discharged from the discharge valve 11 and the discharge valve 13 to be packaged. The hollow glass microsphere of the invention:
(SiO2＋B2O3)/R2O ≥2.5
the particle size is less than or equal to 50um
The water content is less than or equal to 2.0 percent
The volume weight is 0.0-0.2 g/cm3
The breaking rate is less than or equal to 3 percent
The object of the invention is also achieved by the following measures:
the ammonium polyborate solution A can be ammonium pentaborate aqueous solution, and a cheap preparation method comprises the following steps: after boric acid is dissolved in hot water, industrial ammonia water is added, and the reaction equation is as follows:
the solution B in the invention is economic in using sodium silicate aqueous solution, SiO2∶Na2O is preferably 2.4-3.2: 1, and the content of sodium silicate in the sodium silicate aqueous solution is between 30% and 40%.
The invention is that when the solution A and the solution B are mixed, irreversible gel is easy to generate, one mixing method capable of preventing the irreversible gel from generating is to strengthen the dispersion of the solution A in the solution B, firstly, the solution B is added into a proportioning tank 3, and then the solution A is pumped into the solution B from bottom to top through a spray head at the lower part of the proportioning tank 3 under the strong stirring of compressed air. The solution A and the solution B are mixed evenly in time, thereby avoiding the generation of irreversible gel.
In the method for manufacturing the hollow glass microspheres, the adopted waterproof agent is silicon oil emulsion containing 18-22% of silicon oil, and the addition amount of the waterproof agent is preferably 1.0-3.0% of the total amount of the mixed solution before spray drying; the water-proofing agent used in the invention is added into the mixed liquid for spray drying, thus the complex steps of balling and drying and then surface treatment to attach a small amount of water-proofing agent in the traditional process are saved, and the water-proofing effect is obvious. The balling rate is improved, thereby reducing the oil absorption of the product.
The method for manufacturing the hollow glass microspheres adopts a secondary air atomizing nozzle with the primary air pressure of 0.3-0.6 MPa and the secondary air pressure of 0.6-0.2 MPa. The temperature of the hot air can be properly adjusted according to the feeding speed and the requirement of the granularity of the microspheres.
One of the most obvious characteristics of the method for manufacturing the hollow glass microspheres is that the materials are atomized by secondary air and enter a spray drying tower, and then are upward pelletized and dried once along with the hot air introduced from the bottom of the tower, wherein the moisture content is less than 2.0 percent, and secondary drying is not needed, so that the process is simplified, and the energy is saved. And the secondary air atomization balling rate is high, the granularity is fine and uniform, so the strength is high, and the oil absorption is low.
The temperature of hot air introduced from the spray drying tower is generally 350-600 ℃, the air enters the spray drying tower after being heated by a hot blast stove, and the heat source of the heating furnace is from burning coke andcoal gas or preferably an electric furnace.
The drawings of the drawings are illustrated below:
FIG. 1 is a flow chart of a process for manufacturing hollow glass microspheres
1. A solution A preparation tank; 2. a pump; 3. a dosing tank; 4. a pump; 5. a hot blast stove; 6. a blower; 7. inserting plates; 8. a spray drying tower; 9. a secondary air atomizing nozzle; 10. a primary separator; 11. a discharge valve; 12. a secondary separator; 13. a discharge valve; 14. an induced draft fan; 15. an air compressor; 16. a buffer tank; 17. and a mixed liquid storage tank.
FIG. 2, secondary air atomizing nozzle
18. A primary air inlet pipe; 19. an orifice plate; 20. a spray head; 21. a secondary air inlet pipe; 22. and (4) feeding a pipe.
The invention will be further described in detail with reference to the following examples:
example 1:
adding 56kg of tap water and 4kg of boric acid into the solution A preparation tank 1, heating and stirring to dissolve the boric acid and adding 4kg of ammonia (18%), and stirring uniformly for later use to obtain a solution A; 100kg (SiO)2∶Na2O ═ 3.0) sodium silicate solution (solution B) was added to the batching tank 3; stirring the solution A by compressed air, pumping the solution A into the solution B by a pump 2, simultaneously adding 1.5kg of silicone oil emulsion (20 percent), uniformly stirring, pumping the mixed solution into a mixed solution storage tank 17 by a pump 4, and preparing for spray drying; then, sequentially opening the blankA press 15 and a draught fan 14, wherein the primary air pressure is controlled tobe 0.5-0.6 MPa, the secondary air pressure is controlled to be 0.2-0.3 MPa, the temperature at the bottom of the tower is 500 +/-20 ℃, the flow of the mixed solution is 70 kg/h, the temperature at the top of the spray drying tower is 100-160 ℃, and the hollow glass microspheres are obtained;
SiO270.3％
Na2O 23.4％
B2O35.3％
H2O 1.0％
(SiO2＋B2O3)/Na2O 3.23
product granularity ∠ 50um
The volume weight is 0.10g/cm3
The breaking rate is ∠ 3%
Example 2
The preparation method comprises the following steps of example 1:
sodium silicate Solution (SiO)2∶Na2O＝2.4) 100kg
Boric acid 3kg
Ammonia (18%) 3kg
40kg of tap water
2.2kg of silicone oil emulsion (18%)
The process conditions are as follows:
the temperature of hot air entering the tower is 450 +/-20 DEG C
The outlet temperature of the tower top is 100 ℃ to 140 DEG C
The primary air pressure is 0.3-0.4 MPa
The secondary air pressure is 0.2-0.3 MPa
The feed rate was 100 kg/hour
And (3) product analysis results:
SiO367.1％
Na2O27.9％
B2O34.0％
H2O 1.0％
(B2O3＋SiO2)/Na2O 2.55
the particle size is less than or equal to 50um
The volume weight is 0.15g/cm3
The breaking rate is ∠ 2%
Example 3
According to the steps of the embodiment 1, the raw materials are proportioned as follows:
sodium silicate Solution (SiO)2∶Na2O＝3) 100kg
Boric acid 2kg
2kg of ammonia water (19%)
20kg of tap water
Silicone oil emulsion (20%) 3kg
The process conditions are as follows:
the temperature of hot air entering the tower is 400 +/-20 DEG C
The outlet temperature of the tower top is 100 ℃ to 120 DEG C
Primary air pressure 0.5MPa
Secondary air pressure 0.3MPa
The feed rate was 60 kg/hour
And (3) product analysis results:
SiO271.4％
Na2O 23.8％
B2O32.7％
H2O 2.0％
(SiO2＋B2O3)/Na2O 3.11
particle size ∠ 50um
The volume weight is 0.18g/cm3
The breaking rate is ∠ 2%
Compared with the prior art, the invention has the following advantages:
1. the process is simple, the cost is low, and the energy is saved;
2. the hollow glass microspheres have high balling rate, and the waterproof agent is added, so that the chemical stability is good and the oil absorption is low;
3. fine and uniform granularity and high strength;
4. the volume weight is smaller.
Claims (10)
1. The method for manufacturing the hollow glass microspheres is characterized by comprising the following steps of:
a. preparing an ammonium polyborate aqueous solution A;
b. preparing an alkali metal silicate aqueous solution B;
c. mixing the solution A and the solution B, and adding a waterproof agent;
d. the hollow glass microspheres are obtained by primary balling and drying by adopting a secondary air atomizing nozzle;
(SiO2＋B2O3)/R2O ≥2.5
the particle size is less than or equal to 50um
The water content is less than or equal to 2.0 percent
The volume weight is 0.1-0.29/cm3
The breaking rate is less than or equal to 3 percent
2. A method for producing hollow glass microspheres as claimed in claim 1, wherein the solution A is an aqueous solution of ammonium pentaborate, and is inexpensively produced by reacting industrial ammonia with boric acid.
3. The method for producing hollow glass microspheres as claimed in claim 1, wherein the solution B is an aqueous solution of sodium silicate, SiO2∶Na2O is 2.4: 1-3.2: 1; the sodium silicate solution contains 30 to 40 percent of sodium silicate.
4. The method for preparing hollow glass microspheres as claimed in claim 1, wherein a mixing method capable of preventing irreversible gelation from occurring is to add the solution B into a compounding tank, and then to pump the solution A into the solution B from bottom to top through a nozzle at the lower part of the compounding tank under the agitation of compressed air.
5. The method for producing hollow glass microspheres according to claim 1, wherein the water repellent agent is a silicone oil emulsion.
6. The method for producing hollow glass microspheres according to claim 5, wherein the silicone oil emulsion has a silicone oil concentration of 18% to 22%, and the amount of silicone oil added is preferably 1.0% to 3.0% by weight based on the total weight of the mixture.
7. The method for producing hollow glass microspheres as claimed in claim 1, wherein the primary air pressure of the secondary air atomizing nozzle is 0.3 to 0.6MPa, and the secondary air pressure is 0.6 to 0.2 MPa.
8. The method for producing hollow glass microspheres according to claim 1, wherein the material atomized by the secondary air atomizing nozzle is subjected to primary sphere drying by downstreamcontact with hot air introduced from the bottom of the spray drying tower.
9. The method for producing hollow glass microspheres according to claim 1 or claim 9, wherein the temperature of the hot air introduced from the bottom of the spray drying tower is 350 ℃ to 600 ℃.
10. The method for producing hollow glass microspheres as claimed in claim 1, wherein the heat source for spray drying is a coke oven, a gas oven, or an electric oven.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94114205 CN1123772A (en) | 1994-11-29 | 1994-11-29 | Manufacture of hollow glass micro-ball |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94114205 CN1123772A (en) | 1994-11-29 | 1994-11-29 | Manufacture of hollow glass micro-ball |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1123772A true CN1123772A (en) | 1996-06-05 |
Family
ID=5037117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94114205 Pending CN1123772A (en) | 1994-11-29 | 1994-11-29 | Manufacture of hollow glass micro-ball |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1123772A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360442C (en) * | 2005-07-11 | 2008-01-09 | 张伟 | Hollow microbead preparation method |
| CN101585892B (en) * | 2008-05-22 | 2010-09-29 | 中国科学院化学研究所 | Method for preparing polymeric microspheres |
| WO2010121488A1 (en) * | 2009-04-21 | 2010-10-28 | 河北勇龙邦大新材料有限公司 | Method and device for producing hollow microspheres |
| WO2011097777A1 (en) * | 2010-02-10 | 2011-08-18 | 浙江通达机械有限公司 | Preparation method of hydrophobic hollow glass micro bead and hydrophobic hollow glass micro bead thereof |
| CN101039871B (en) * | 2004-09-21 | 2011-11-02 | 萨凡纳河核能解决方案有限公司 | Hollow porous-wall glass microspheres for hydrogen storage |
| CN105588418A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Device and method for preventing wall adhesion of spray drying tower |
| CN106081630A (en) * | 2016-08-11 | 2016-11-09 | 葛洲坝易普力四川***工程有限公司 | Glass microsphere induction system |
| CN108191250A (en) * | 2018-03-30 | 2018-06-22 | 山东德润机电设备制造有限公司 | Hollow glass micropearl and preparation method thereof |
| IT202000029822A1 (en) * | 2020-12-04 | 2022-06-04 | Consulchem Di Capra Vittorio | PROCEDURE FOR THE TREATMENT OF A RINDED CHEESE |
-
1994
- 1994-11-29 CN CN 94114205 patent/CN1123772A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101039871B (en) * | 2004-09-21 | 2011-11-02 | 萨凡纳河核能解决方案有限公司 | Hollow porous-wall glass microspheres for hydrogen storage |
| CN100360442C (en) * | 2005-07-11 | 2008-01-09 | 张伟 | Hollow microbead preparation method |
| CN101585892B (en) * | 2008-05-22 | 2010-09-29 | 中国科学院化学研究所 | Method for preparing polymeric microspheres |
| EA020857B1 (en) * | 2009-04-21 | 2015-02-27 | Хэбэй Ил-Банда Нью Матириалз Лимитед Компани | Method for producing hollow microspheres |
| WO2010121488A1 (en) * | 2009-04-21 | 2010-10-28 | 河北勇龙邦大新材料有限公司 | Method and device for producing hollow microspheres |
| US8845936B2 (en) | 2009-04-21 | 2014-09-30 | Hebei Yl-Bangda New Materials Limited Company | Process and device for the preparation of hollow microspheres comprising centrifugal atomization |
| WO2011097777A1 (en) * | 2010-02-10 | 2011-08-18 | 浙江通达机械有限公司 | Preparation method of hydrophobic hollow glass micro bead and hydrophobic hollow glass micro bead thereof |
| CN105588418A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Device and method for preventing wall adhesion of spray drying tower |
| CN105588418B (en) * | 2014-10-21 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of device and method for preventing spray drying tower from gluing wall |
| CN106081630A (en) * | 2016-08-11 | 2016-11-09 | 葛洲坝易普力四川***工程有限公司 | Glass microsphere induction system |
| CN108191250A (en) * | 2018-03-30 | 2018-06-22 | 山东德润机电设备制造有限公司 | Hollow glass micropearl and preparation method thereof |
| IT202000029822A1 (en) * | 2020-12-04 | 2022-06-04 | Consulchem Di Capra Vittorio | PROCEDURE FOR THE TREATMENT OF A RINDED CHEESE |
| EP4008188A1 (en) | 2020-12-04 | 2022-06-08 | Consulchem di Capra Vittorio | Process for the treatment of rinded cheese |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2594611B1 (en) | Method for preparing white carbon black modified by silane coupling agent | |
| CN101880482B (en) | Method for modifying nano metal oxide by coupling graft | |
| CN1036658C (en) | Spheroid silicon dioxide, process of preparation and use for reinforced elastic body thereof | |
| CN1025749C (en) | Method for preparing pellet sintered ore | |
| CN105417566A (en) | Method for preparing nano calcium carbonate through full-automatic rotating pressure jet-carbonation technology | |
| CN1123772A (en) | Manufacture of hollow glass micro-ball | |
| CN104403433B (en) | The preparation method of the special winnofil of PVC stone-impact-proof paint | |
| CN1764600A (en) | Pyrogenic silicon dioxide powder and dispersion thereof | |
| CN1068975A (en) | The preparation method of low-density, large pore volume, high-strength alumina carrier | |
| CN1903898A (en) | Siloxane containing water soluble polymer emulsion and redispersible emulsion powder and its preparation method | |
| CN1173018C (en) | Coal briquette having superior strength and briquetting method thereof | |
| WO2021073060A1 (en) | Method for preparing hollow glass microbeads with high floatation rate | |
| CN1660917A (en) | Modification method for graft polymerization of acrylic ester of silicane coupled to Nano SiO2 | |
| CN107381611B (en) | A kind of artificial stone's modified nano calcium carbonate powder and preparation method thereof and resin based artificial stone material | |
| CN110395753A (en) | A kind of preparation method of epigranular high stable houghite | |
| CN104591195B (en) | Method of preparing white carbon black by virtue of carbonization method | |
| CN1757668A (en) | High molecule/calcium carbonate nanometer particles, functional particles and prepn. method thereof | |
| CN107601828B (en) | Hollow glass microsphere and preparation method thereof | |
| CN113666380A (en) | Preparation method of spherical silicon dioxide | |
| CN107254239B (en) | A kind of composite modified fluorine carbon polyester powdery paints and preparation method thereof | |
| CN1159226C (en) | Process for preparing rare-earth nano oxide by ball grinding and solid-phase chemical reaction | |
| CN114408958B (en) | Device and method for preparing hollow spherical calcium carbonate and hollow spherical calcium carbonate prepared by using device | |
| CN104607172B (en) | Preparation method of Ce-doped plasma catalyst | |
| CN213569554U (en) | Magnesium nitrate pyrolysis device based on resource cyclic utilization | |
| CN107010626A (en) | A kind of method that carbonaceous raw material prepares pelletizing method carbide raw material with quick lime mixed-forming |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |