CN101585540B - Prepartion method of silicon dioxide with high pore volume - Google Patents
Prepartion method of silicon dioxide with high pore volume Download PDFInfo
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- CN101585540B CN101585540B CN2009101121271A CN200910112127A CN101585540B CN 101585540 B CN101585540 B CN 101585540B CN 2009101121271 A CN2009101121271 A CN 2009101121271A CN 200910112127 A CN200910112127 A CN 200910112127A CN 101585540 B CN101585540 B CN 101585540B
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- pore volume
- pure water
- silicic acid
- dioxide
- propyl carbinol
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Abstract
The invention discloses a prepartion method of silicon dioxide with high pore volume, which uses soluble sodium silicate as materials to produce a silicic acid of certain concentration by ion exchange, in neutralization reaction with ammonia water, ammonia water is added as auxiliary for enlarging pores, carbowax is added as surface active agent to synthesize slurry with high pore volume, through filter pressing, washing, replacement of organic solvents, dried distillation with added butanol solid pore, calcination and fluid energy milling to obtain silica ultra-fine powder with high pore volume and uniform particle, and obtained silicon dioxide has little impurity, high oil adsorption value and high pore volume, which can be used in middle-high grade paint with good extinction performance, high transparency and no yellowing.
Description
One, technical field
The present invention relates to fine chemistry industry powder body material preparation method, the preparation method of the silica-based matting agent of particularly high pore volume.
Two, background technology
Silicon-dioxide uses when being applied to coating as matting agent, and the most important technical indicator that influences eliminate optical property is the pore volume of silicon-dioxide, and the high more eliminate optical property of pore volume value is good more.At present, the preparation method that silica-based matting agent generally adopts is to be that raw material carries out precipitin reaction with alkaline silicate and acid, makes micron silica through ageing, filtration, washing, drying, pulverizing then; The product quality indicator that makes is: pore volume 0.4cm
3/ g～1.8cm
3/ g, BET specific surface area 130m
2/ g～300m
2/ g, mean pore size 180A～300A, DBP absorption value 2.0ml/g～3.0ml/g, size distribution D50:2.0 μ m～10.0 μ m, because of pore volume and oil-absorption(number) are lower, foreign matter content height, the coating of production exist that eliminate optical property is low, poor transparency, easy xanthochromic shortcoming.The preparation method of another kind of silicon-dioxide is a sol-gel method, it is that tetraethyl silicate and dehydrated alcohol are stirred into uniform mixed solution by certain mol proportion, in stirring, slowly add proper amount of deionized water, then with the pH value of ammoniacal liquor or hydrochloric acid conditioning solution, add an amount of tensio-active agent again, the reaction certain hour obtains white powder-like product after ageing, washing, drying; The product quality indicator that makes has certain improvement than the former, but owing to there are not the counter-boring techniques means, its main capability and performance index such as pore volume numerical value are still on the low side, can not solve effectively that the Coating Matting performance is low, poor transparency, easy xanthochromic problem, and have that the highly seasoned pollution of tetraethyl silicate is big, solvent consumption is big, production cost is high in the preparation process shortcoming.And prepare silicon-dioxide because investment is big, cost is high with vapor phase process, can't popularize.
Three, summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high-performance silicon dioxide class matting agent, eliminate optical property height when not only being applied to middle and high shelves coating, good, the anti-xanthochromia of transparency are good, and this matting agent cost of manufacture is low, making processes is pollution-free.
For realizing above purpose, the present invention adopts soluble glass to make raw material, being that precipitation agent, bicarbonate of ammonia are that expanding agent, polyoxyethylene glycol are to carry out building-up reactions under the condition of tensio-active agent with ammoniacal liquor, behind press filtration, washing, organic solvent displacement, solid orifice drying, calcining and comminution by gas stream, obtain pore volume greater than 2.0cm
3The silica product of/g, concrete steps are as follows:
The first step: water glass refining
Solid solubility water glass and pure water are pressed (3～4): 10 weight ratio is at 4kgf/cm
2～6kgf/cm
2Vapor pressure is dissolving down, after natural subsidence is abundant, gets supernatant liquid and is made into concentration 8 with pure water
0B é～10
0Rare sodium silicate solution of B é, standby after sheet frame circulation agitation and filtration removes slag.
Second step: the preparation of silicic acid
To filter concentration is 8
0B é～10
0The water glass of B é carries out ion-exchange by the highly acidic cation exchange column, presses 0.8m
3/ h～1.5m
3It is rare silicic acid of 2%～3% that the flow velocity of/h is produced concentration, and it is standby to enter test tank.
The 3rd step: silicon-dioxide synthetic
Pure water, bicarbonate of ammonia and polyoxyethylene glycol are dropped into reactor successively under condition of stirring, after stirring, add concentration again and be 15%～20% ammoniacal liquor, drip rare silicic acid and carry out building-up reactions, rate of addition control 1.8m
3/ h～2.0m
3/ h after adding, is warming up to 78 ℃～85 ℃, continues reaction 80min～100min, is that 13～14 backs are aging to the material pH value, obtains silica slurry.Each weight ratio that adds material is rare silicic acid (17～23): pure water (8～10): bicarbonate of ammonia (0.5～0.6): polyoxyethylene glycol (0.07～0.08): ammoniacal liquor (0.5～0.6).
The chemical equation of this building-up reactions is:
The 4th step: press filtration, washing
Aging good slurry is injected sheet frame, carries out solid-liquid and separate, and with the pure water washing leaching cake to PH=7～8.
The 5th step: slurrying, liquefaction
The filter cake that washing is good is put into pulping tank, adds propyl carbinol, by weight propyl carbinol: rare silicic acid=(4.0～6.5): the quantity of (17～23) adds, and liquefies through high-speed stirring slurrying.
The 6th step: dehydration, solid hole
Material after the liquefaction is injected in the still kettle, add solid hole agent propyl carbinol again, quantity feeds steam with last time suitable, under vacuum condition, carries out azeotropic distillation, slowly promotes moisture content.
The 7th step: dry and calcining
Material after dewatering is injected dry still, feed steam and carry out vacuum-drying, reclaim propyl carbinol simultaneously.Dried material obtains white powdery work in-process through calcining.
The 8th step: comminution by gas stream, classification, packing
It is the 3 μ m～high pore volume superfine silicon dioxide of 5 μ m product that work in-process after the calcining are obtained particle diameter D50 by micronizer mill pulverizing, classification, packing, warehouse-in.
It is raw material that the present invention adopts soluble glass, generate certain density silicic acid by ion-exchange, when carrying out neutralization reaction with ammoniacal liquor, adding bicarbonate of ammonia is made the reaming auxiliary agent, polyoxyethylene glycol is made the synthetic high pore volume slurry of tensio-active agent, adds the solid hole of propyl carbinol, calcining and comminution by gas stream and obtain evengranular high pore volume silicon-dioxide ultrafine powder when press filtration, washing, organic solvent displacement, distillation dehydration, drying.Its concrete quality index is: pore volume 〉=2.0cm
3/ g, BET specific surface area 250m
2/ g～350m
2/ g, DBP absorption value 3.8ml/g～4.5ml/g.
The high pore volume made of silicon dioxide of the present invention method raw materials for production are cheap, making processes is easy to control, constant product quality, the high pore volume silicon-dioxide of producing has that impurity is few, oil-absorption(number) and the high characteristics of pore volume, be used for that middle and high shelves coating eliminate optical property is good, transparency is high, xanthochromia not, provide a kind of high performance matting agent raw material for producing the inferior optical coating of middle and high shelves.
Four, embodiment
Below in conjunction with the concrete example of implementing the present invention is described in further detail.
Embodiment 1
Operation steps is as follows:
(1). making with extra care of water glass
Drop into 1.5 tons of solid solubility water glass to rotary spherical digester, and add 3m
3Pure water feeds steam, at 4kgf/cm
2～6kgf/cm
2Vapor pressure is dissolving down, pressurize blowing after 2 hours, concentration 28
0B é～30
0B é.Put into the storage tank natural subsidence two days, and got 2.8m
3(transparency is that 130mm～150mm) adds 6.0m to supernatant liquid
3Pure water is made into 9
0B é～10
0Rare sodium silicate solution of B é by the sheet frame circulating filtration, is used for ion-exchange.
(2). the preparation of silicic acid
Good 7.0m will be filtered
3Rare sodium silicate solution is strongly acidic styrene's Zeo-karb exchange column of 001 * 7 by model, with 1.5m
3The flow velocity of/h is produced PH and is 2.6～3.0 the about 6.65m of rare silicic acid
3, the time of ion-exchange is 3h～3.5h.
(3). synthesizing of silicon-dioxide
At 5m
3Add pure water 1000kg in the reactor successively, 50kg bicarbonate of ammonia, 8Kg polyoxyethylene glycol after stirring, add 18% ammoniacal liquor 50Kg again, drip rare silicic acid 1.8m of 2%～3%
3Carry out building-up reactions, rate of addition control 2.0m
3/ h after adding, is warming up to 85 ℃, continues reaction 1.5h, to the material pH value be 13～14, aging 0.5h, blowing.
(4). press filtration, washing
Slurry after aging is slowly injected sheet frame in batches, carry out solid-liquid and separate, treat that material feeding pressure reaches 5.5kgf/cm
2The time, stop material feeding, use the pure water washing leaching cake to PH=7～8.
(5). slurrying, liquefaction
The filter cake that washing is good is put into pulping tank for 500 kilograms, adds 1.0m
3Propyl carbinol, slurrying liquefaction under high-speed stirring.
(6). dehydration, solid hole
Material after the liquefaction is pumped into 6m
3In the still kettle, add 2.5m
3Propyl carbinol feeds steam, is under the 0.03MPa condition in vacuum tightness, and azeotropic distillation is slowly promoted moisture content, treat that substantially anhydrous branch steams after, steam off.
(7). dry, calcining
Material after dewatering is injected 5m
3In the dry still, feed steam and carry out vacuum-drying, reclaim propyl carbinol simultaneously.Dried material obtains white powdery work in-process after 650 ℃ of calcinings.
(8). comminution by gas stream, classification, packing
Work in-process after the calcining are collected through pocket type pulsed dust collector by micronizer mill pulverizing, classification, and obtaining particle diameter D50 is the 3 μ m～high pore volume superfine silicon dioxide of 5 μ m product, packs at last, puts in storage.
Embodiment 2
Operation steps is as follows:
A. water glass is refining
Drop into 4 tons of solid solubility water glass to rotary spherical digester, and add 10m
3Pure water feeds steam pressurized to 4kgf/cm
2～6kgf/cm
2Dissolve, 2 hours blowings of pressurize, concentration is 30
0B é.Put into to be with and stir storage tank, by weight 0.5% adding flocculation agent polyacrylamide, sedimentation is one day after stirring, and gets transparency to be 〉=180mm supernatant liquid 2.8m
3, add 6.0m
3Pure water is made into 9
0B é～10
0Rare sodium silicate solution of B é behind the sheet frame circulating filtration, is used for ion-exchange.
B. the preparation of silicic acid
Good 5m will be filtered
3Rare sodium silicate solution is strongly acidic styrene's Zeo-karb exchange column of 001 * 7 by model, with 1.5m
3It is 2.6～3.0 silicic acid 4m that the flow velocity of/h is produced PH
3～4.5m
3, the time of exchange is 2.5h.
C. silicon-dioxide is synthetic
At 5m
3Add pure water 0.9m in the reactor earlier
3, 48kg bicarbonate of ammonia, 7kg polyoxyethylene glycol after stirring, add 18% ammoniacal liquor 55kg again, drip rare silicic acid 2.0m of 2～3%
3Carry out building-up reactions, rate of addition control 1.8m
3/ h～2.0m
3/ h after adding, is warming up to 85 ℃, continues reaction 1.5h, to the material pH value be 13～14, aging 0.5h, blowing.
D. press filtration, washing
Slurry after aging is slowly injected sheet frame in batches, carry out solid-liquid and separate, treat that material feeding pressure reaches 5.5kgf/cm
2The time, stop material feeding, use the pure water washing leaching cake to PH=7～8.
E. slurrying, liquefaction
The filter cake that washing is good is put into pulping tank for 500 kilograms, adds 0.8m
3Propyl carbinol, slurrying liquefaction under high-speed stirring.
F. dewater, consolidate the hole
Material after the liquefaction is pumped into 6m
3In the still kettle, add 2.2m
3Propyl carbinol feeds steam, is slowly to promote moisture content under the 0.03MPa condition in vacuum tightness, treat that substantially anhydrous branch steams after, steam off.
G. dry, calcining
Material after dewatering is injected 5m
3In the dry still, feed steam and carry out vacuum-drying, reclaim propyl carbinol simultaneously.Dried material obtains white powdery work in-process after 650 ℃ of calcinings.
H. comminution by gas stream, classification, packing
Work in-process after the calcining are collected through pocket type pulsed dust collector by micronizer mill pulverizing, classification, and obtaining particle diameter D50 is the 3 μ m～high pore volume superfine silicon dioxide of 5 μ m product, packs at last, puts in storage.
Silica product that two embodiment make and the contrast of U.S. ED3 technical target of the product are as follows:
| The mensuration project | Embodiment 1 | Embodiment 2 | ED3 (U.S.) |
| Dioxide-containing silica (butt), % | 99.6 | 99.7 | 99.0 |
| Weight loss on heating (105 ℃), % | 2.00 | 2.12 | 2.0 |
| PH (10% suspension) | 4.25 | 4.05 | 7.0 |
| The DBP absorption value, ml/g | 4.12 | 4.05 | 3.2 |
| Specific surface area, m 2/g | 372 | 374.8 | 256 |
| Pore volume, cm 3/g | 2.458 | 2.547 | 1.8 |
| Iron level, % | 0.0078 | 0.0055 | 0.013 |
| Particle diameter; D50, μ m | 3.3 | 3.6 | 3.0 |
As seen, more than two embodiment can obtain high pore volume silica product, the charging capacity minor variations is little to quality product influence.But add in the embodiment 2 refining soluble water glass processes polyacrylamide flocculant can improve raw material transparency, reduce foreign matter content, the product purity that obtains, pore volume and oil-absorption(number) are all greater than ED3.
Claims (1)
1. the preparation method of a high pore volume silicon-dioxide after making silica slurry, carries out filter press, pure water washing, steam-to-vacuum drying, is sintered into white powdery work in-process, micronizer mill is pulverized with divide grade packagedly, obtains pore volume greater than 2.0cm
3The silicon-dioxide of/g is characterized in that: described silica slurry is to adopt soluble glass to make raw material, with ammoniacal liquor be precipitation agent, bicarbonate of ammonia be expanding agent, polyoxyethylene glycol be carry out under the condition of tensio-active agent building-up reactions and aging after make; Before silicon-dioxide drying, calcining, adopt the solid hole of propyl carbinol to handle; The relating operation step is as follows:
Making with extra care of water glass: solid solubility water glass and pure water are pressed (3～4): 10 weight ratio is at 4kgf/cm
2～6kgf/cm
2Vapor pressure is dissolving down, after natural subsidence is abundant, gets supernatant liquid and is made into concentration 8 with pure water
0B é～10
0Rare water glass of B é, standby after sheet frame circulation agitation and filtration removes slag;
The preparation of silicic acid: will filter concentration is 8
0B é～10
0The water glass of B é carries out ion-exchange by the highly acidic cation exchange column, presses 0.8m
3/ h～1.5m
3It is rare silicic acid of 2%～3% that the flow velocity of/h is produced concentration, and it is standby to enter test tank;
Silicon-dioxide synthetic: pure water, bicarbonate of ammonia and polyoxyethylene glycol are dropped into reactor successively under condition of stirring, after stirring, add concentration again and be 15%～20% ammoniacal liquor, drip rare silicic acid and carry out building-up reactions, rate of addition control 1.8m
3/ h～2.0m
3/ h after adding, is warming up to 78 ℃～85 ℃, continues reaction 80min～100min, is that 13～14 backs are aging to material pH value, obtains silica slurry; Each weight ratio that adds material is rare silicic acid (17～23): pure water (8～10): bicarbonate of ammonia (0.5～0.6): polyoxyethylene glycol (0.07～0.08): ammoniacal liquor (0.5～0.6);
Handle in the solid hole of propyl carbinol: at silica slurry process filter press, filter cake after the pure water washing is put into pulping tank, by weight propyl carbinol: rare silicic acid=(4.0～6.5): the quantity of (17～23) adds propyl carbinol, liquefy through high-speed stirring slurrying, again the material after the liquefaction is injected in the still kettle, add solid hole agent propyl carbinol, quantity is with last time suitable, feed steam, under vacuum condition, carry out azeotropic distillation, slowly promote moisture content, in drying process subsequently, reclaim propyl carbinol, enter calcining again, comminution by gas stream, classification and packaging process, obtaining particle diameter D50 is the 3 μ m～high pore volume superfine silicon dioxide of 5 μ m product.
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| EP3168191B1 (en) * | 2011-09-16 | 2018-06-20 | Nissan Chemical Industries, Ltd. | Method for producing purified active silicic acid solution and silica sol |
| CN103101918B (en) * | 2011-11-10 | 2017-07-21 | 常州英中纳米科技有限公司 | A kind of method that carbon coating prepares single dispersing crystalline silica spheric granules |
| CN102583405B (en) * | 2012-03-23 | 2013-10-23 | 山东大学 | Method for preparing pore diameter adjustable mesoporous silica nanoparticles |
| CN102633272A (en) * | 2012-04-19 | 2012-08-15 | 浙江宇达化工有限公司 | Preparation method of precipitated silicon dioxide |
| CN102911529B (en) * | 2012-09-27 | 2014-01-15 | 中国海洋石油总公司 | Preparation method of silicon dioxide for polyethylene anti-block masterbatch in high add amount |
| CN103803566B (en) * | 2014-03-10 | 2015-09-30 | 福建正盛无机材料股份有限公司 | The preparation method of transparent rubber strengthening agent precipitated silica |
| CN108314053B (en) * | 2016-07-20 | 2020-01-03 | 福建远翔新材料股份有限公司 | Preparation method of silicon dioxide for hydrophobically modified super heat-insulating material |
| CN107162006B (en) * | 2017-05-25 | 2019-05-24 | 厦门大学 | One kind plus salt drying means |
| CN110299450B (en) * | 2018-03-23 | 2021-03-26 | 中国科学院物理研究所 | Preparation method of flexible porous carbon counter electrode and perovskite type solar cell |
| CN110143599A (en) * | 2019-04-08 | 2019-08-20 | 杭州电子科技大学 | A kind of macropore appearance SiO2The novel preparation method of material |
| CN114597384B (en) * | 2021-12-30 | 2023-06-23 | 深圳技术大学 | Method for preparing lithium ion battery cathode material by utilizing crystalline silicon wire saw waste mortar |
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| US20030065112A1 (en) * | 1997-11-14 | 2003-04-03 | Rimantas Glemza | High pore volume polyolefin catalyst |
| CN1418811A (en) * | 2002-12-18 | 2003-05-21 | 天津化工研究设计院 | Macroporous precipitation silicon dioxide used for achromatic colours, and its prepn. method |
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| US20030065112A1 (en) * | 1997-11-14 | 2003-04-03 | Rimantas Glemza | High pore volume polyolefin catalyst |
| CN1418811A (en) * | 2002-12-18 | 2003-05-21 | 天津化工研究设计院 | Macroporous precipitation silicon dioxide used for achromatic colours, and its prepn. method |
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