CN103936014B - A kind of preparation method of white carbon black - Google Patents
A kind of preparation method of white carbon black Download PDFInfo
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- CN103936014B CN103936014B CN201410175798.3A CN201410175798A CN103936014B CN 103936014 B CN103936014 B CN 103936014B CN 201410175798 A CN201410175798 A CN 201410175798A CN 103936014 B CN103936014 B CN 103936014B
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- carbon black
- white carbon
- starch
- water glass
- glass solution
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- 239000006229 carbon black Substances 0.000 title claims abstract description 101
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920002472 Starch Polymers 0.000 claims abstract description 55
- 239000008107 starch Substances 0.000 claims abstract description 55
- 235000019698 starch Nutrition 0.000 claims abstract description 55
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 51
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000003756 stirring Methods 0.000 claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000011089 carbon dioxide Nutrition 0.000 claims abstract description 25
- 238000003763 carbonization Methods 0.000 claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 claims abstract description 24
- 238000005507 spraying Methods 0.000 claims abstract description 22
- 238000001694 spray drying Methods 0.000 claims abstract description 21
- 238000005469 granulation Methods 0.000 claims abstract description 11
- 230000003179 granulation Effects 0.000 claims abstract description 11
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 22
- 240000003183 Manihot esculenta Species 0.000 claims description 6
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 6
- 235000013312 flour Nutrition 0.000 claims description 6
- 229940100486 rice starch Drugs 0.000 claims description 6
- 244000017020 Ipomoea batatas Species 0.000 claims description 5
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 5
- 229920001592 potato starch Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 244000068988 Glycine max Species 0.000 claims description 4
- 235000010469 Glycine max Nutrition 0.000 claims description 4
- 240000006394 Sorghum bicolor Species 0.000 claims description 4
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 27
- 229920001971 elastomer Polymers 0.000 abstract description 24
- 239000005060 rubber Substances 0.000 abstract description 24
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000013329 compounding Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 17
- 238000005987 sulfurization reaction Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- FWGRZUQTHDIFFA-UHFFFAOYSA-M [Cl-].[NH4+].C(CCCCCCCCCCCCCCC)C[N+](C)(C)C.[Cl-] Chemical compound [Cl-].[NH4+].C(CCCCCCCCCCCCCCC)C[N+](C)(C)C.[Cl-] FWGRZUQTHDIFFA-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 activated silica alcohol radical Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-DVKNGEFBSA-N alpha-D-glucose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-DVKNGEFBSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- KENBDIBVUKXMTB-UHFFFAOYSA-N heptadecyl(trimethyl)azanium Chemical compound CCCCCCCCCCCCCCCCC[N+](C)(C)C KENBDIBVUKXMTB-UHFFFAOYSA-N 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910021331 inorganic silicon compound Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IITYNULCUHDIAI-UHFFFAOYSA-M trimethyl(nonadecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCC[N+](C)(C)C IITYNULCUHDIAI-UHFFFAOYSA-M 0.000 description 1
- OHCYZUDVCRJREC-UHFFFAOYSA-M trimethyl(pentadecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCC[N+](C)(C)C OHCYZUDVCRJREC-UHFFFAOYSA-M 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- VCOYQLVGJRYNFY-UHFFFAOYSA-M trimethyl(tridecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)C VCOYQLVGJRYNFY-UHFFFAOYSA-M 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Abstract
The present invention relates to a kind of method of preparation of novel white carbon black, following steps involved in the present invention: by certain modulus, water glass solution containing finite concentration quaternary ammonium salt and starch, stir in certain temperature with under stirring, pass in spray-drying tower with carbonic acid gas reaction in－situ, spraying dry obtains white carbon black finished product, by finished product carbonization at a certain temperature, or carbonization after granulation.Method equipment requirements involved in the present invention is simple, and raw material is simple and easy to get, with low cost, quick and high efficient reaction, environmental friendliness, and the novel white carbon black of generation has unique characteristic, meets rubber white carbon black property indices, has good economic benefit.
Description
Technical field
The present invention relates to a kind of preparation method of novel white carbon black.The method that the present invention adopts carbonic acid gas and amyloid water glass solution to carry out reaction in－situ in the reaction tower of spray-drier prepares novel white carbon black, spraying dry directly obtains novel white carbon black finished product, the inventive method is swift in response, and efficiency is high and meet energy-conserving and environment-protective demand.
Background technology
At present, in domestic and international white carbon black industry, the white carbon black technique of preparing having realized industry words mainly contains vapor phase process and the precipitator method.The production method of usual domestic high-quality white carbon black mainly uses vapor phase process, but due to complex process, facility investment is large, and raw material is not easy to obtain, high in cost of production shortcoming, limits the white carbon black heavy industrialization of high-quality.And although common acid precipitation method is with low cost, white carbon black quality does not reach the demand in market mostly.
In general, white carbon black and hydrated SiO 2, structural formula is SiO
2nH
2o, has special surface tissue (with surface hydroxyl and planar water), special particle form (particle is little, specific surface area is large) and unique physical and chemical performance.Thus white carbon black have porousness, polymolecularity, light weight, chemical stability good, high temperature resistant, do not burn, the important inorganic silicon compound of the excellent properties such as electrical insulating property is good.Such characteristic makes white carbon black be widely used in the numerous areas such as rubber, plastics, coating, medicine, daily-use chemical industry.
The white carbon black in the current whole world 70% is used for rubber industry, be excellent rubber reinforcing filler, can improve cementing property and tear strength, and its performance is obviously better than ordinary carbon black.
But the activated silica alcohol radical that poly-silica and outside surface due to traditional white carbon black inside exist and planar water characteristic thereof, make it be wetting ability, and after white carbon black being added into the materials such as rubber, white carbon black is difficult to moistening in organic phase and dispersion.And because white carbon black surface exists hydroxyl, surface energy is comparatively large, and aggregate always tends to cohesion, and thus the application performance of product is affected.
Industrial is often hydrophobicity to the requirement of white carbon black, but shows very strong wetting ability containing a large amount of silicone hydroxyl due to white carbon black surface, therefore improves its interface binding power with polymeric compositions, needs to carry out surface modification to it.Usual method is: utilize suitable chemical substance to make it to react with the hydroxyl on white carbon black surface by certain processing method, eliminates and the amount reducing surface silanol groups, makes the wetting ability of product change into hydrophobicity, to reach the object of modification.At present, use method of modifying the most general to have the polymer graft method of alcohol esterification process, reactive organic silicon compound method, particle surface, also have in addition and diazomethane reaction and halogen reaction, and silicon chlorides reaction etc.But these Chemical Process Feedstock are expensive, and complex process, reacts wayward, therefore also defines it and realizes industrialization.
The preparation method of Chinese patent a kind of starch/white carbon black compounded mix, the white carbon black method of modifying related to white carbon black is mixed into the blending modification method in the good starch paste of gelatinization in advance, this method technique is simple, be easy to realize, but be only the modification to white carbon black finished product, coated between starch and white carbon black is simple absorption.
The polysaccharide polymer compound that starch is made up of a-D-glucose, molecular formula is (C
6h
10o
5)
n, its molecular structure has straight-chain and branched two kinds, and it is a kind of crystal material of strong polar polyhydroxy.In each glucose building blocks of starch molecule 2,3, containing hydroxyl on 6 carbon, have these to have chemically active hydroxyl, so can with chemical compound lot generation grafting, crosslinking reaction, this makes to carry out modification to starch becomes possibility.Therefore, starch is incorporated in the modification of white carbon black, by in-situ method, makes starch and white carbon black generation chemical action, obtained novel white carbon black, the current rare people's research of such method.
Summary of the invention
The present invention relates to a kind of preparation method of novel white carbon black, in the spray drying tower, pass into water glass solution containing starch and carbon dioxide reaction prepares novel white carbon black, spraying dry obtains the coated white carbon black finished product of starch.The problems such as such method fundamentally solves white carbon black and easily reunites, difficult dispersion.Adopt carbonic acid gas and the water glass solution containing starch to be generated the technique of novel white carbon black by spraying dry direct in-situ, finally obtain starch conversion white carbon black.
A kind of preparation method of white carbon black, it is characterized in that: be 2.4 ~ 3.8 by modulus, mass concentration is the water glass solution of 5% ~ 25%, add the starch of the quaternary ammonium salt of 0.01% ~ 0.1% of water glass solution quality and 2% ~ 25% of water glass solution quality, low whipping speed is 50m/min ~ 300m/min and temperature is under 60 ~ 95 DEG C of conditions, stirring and passing into inlet air temperature after gelatinization is evenly 200 ~ 700 DEG C, temperature out is the gas reaction in－situ in the spray-drying tower of 70 ~ 140 DEG C and containing 10 ~ 100% carbonic acid gas, spraying dry obtains novel white carbon black finished product, carbonization is carried out at 200 ~ 300 DEG C, or carbonization at 180 ~ 250 DEG C after granulation.
As preferably: starch used is glutinous rice starch, W-Gum, pea starch, tapioca (flour), sweet potato starch, soybean starch, sorghum starch, and starch consumption is 2% ~ 25% of water glass quality.
As preferably: the quaternary ammonium salt used for main chain be the quaternary ammonium salt of 12 to 18 containing carbon number, itself and water glass solution mass ratio are 0.01% ~ 0.1%.
As preferably: spray-dired atomizing particle size is 5 ~ 100 microns, and inlet air temperature is 200 ~ 700 DEG C, and temperature out is 70 ~ 140 DEG C.
Use in-situ method to carry out starch conversion white carbon black, its mechanism is: first fully dissolved by quaternary ammonium salt and be dispersed in water glass solution, makes the abundant gelatinization of starch at a certain temperature in water glass solution.Amyloid water glass good for gelatinization is passed in the spray-drying tower of certain temperature, a large amount of fine mist is atomized under the effect of atomizing disk high speed centrifugation, particle diameter is 5 ~ 100 microns, amyloid water glass solution is under the effect of quaternary ammonium salt, starch in droplet and water glass are uniformly distributed, in dense carbonic acid gas atmosphere, the contact area of carbonic acid gas and water glass is very big, easily make carbonic acid gas and the water glass generation reaction in－situ containing starch, generate the coated white carbon black of starch, final drying obtains novel white carbon black finished product, in the process of reaction, in starch, the hydroxyl on the activated hydroxyl of tool and white carbon black surface is had an effect, starch and white carbon black are reacted, be coated on white carbon black surface equably, reduce white carbon black hydroxy radical content, introduce some characteristics of starch simultaneously, thus define the white carbon black being coated with one deck new texture, finally white carbon black coated for starch is carried out carbonization after carbonization or granulation, thus make this white carbon black have more characteristics.
Containing the novel white carbon black of carbon structure after carbonization, there is electroconductibility, have certain consistency with rubber, have again certain inertia, its structure and carbon black structural similitude, anti-slippery, play the effect of white carbon black.In mixing, the same with carbon black again have consistency.
Beneficial effect
Method involved in the present invention is prepared its advantage of white carbon black and is:
(1) equipment requirements is simple, and process characteristic is applicable to large-scale industrial production.
(2) raw material is simple and easy to get, with low cost.
(3) generate Product size little, be evenly distributed, meet rubber white carbon black property indices.
(4) speed of response is extremely short, substantially increases efficiency.
(5) saving water resource, makes full use of CO 2 waste gas, recycles water resources and carbonic acid gas, has good economic benefit.
(6) the white carbon black easy problem such as reunion, airborne dust is in the polymer solved.
(7) novel white carbon black has unique characteristic.
Embodiment
Embodiment 1:
Be the water glass solution of 3.8 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 10%, add 0.2g Trimethyllaurylammonium bromide, add 2g glutinous rice starch, 30min is stirred under 70 DEG C of heating, stir speed (S.S.) is 100m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 50% compositions are air) containing 50% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 300 DEG C, temperature out 90 DEG C, atomizing particle size is 5 microns, obtain starch conversion white carbon black finished product after spraying dry and carry out carbonization on 200 DEG C of vulcanization beds, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 2:
Be the water glass solution of 2.4 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 15%, add 0.5g Tetradecyl Trimethyl Ammonium Bromide, add 10g W-Gum, 30min is stirred under 68 DEG C of heating, stir speed (S.S.) is 150m/min, abundant stirring passes in spray-drying tower, with the gas (other 80% compositions are nitrogen) containing 20% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 200 DEG C, temperature out 70 DEG C, atomizing particle size is 10 microns, starch conversion white carbon black finished product is obtained after spraying dry, on 180 DEG C of vulcanization beds, carbonization is carried out after granulation, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 3:
Be the water glass solution of 2.8 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 22%, add 1g cetyl trimethylammonium bromide, add 25g tapioca (flour), 30min is stirred under 85 DEG C of heating, stir speed (S.S.) is 180m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 60% compositions are air) containing 40% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 500 DEG C, temperature out 120 DEG C, atomizing particle size is 30 microns, starch conversion white carbon black finished product is obtained after spraying dry, 200 DEG C of rotary drum dryers carry out carbonization, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 4:
Be the water glass solution of 3.1 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 8%, add 0.4g Cetyltrimethylammonium bromide, add 15g soybean starch, 20min is stirred under 80 DEG C of heating, stir speed (S.S.) is 200m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 30% compositions are superheated vapour) containing 70% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 600 DEG C, temperature out 110 DEG C, atomizing particle size is 50 microns, starch conversion white carbon black finished product is obtained after spraying dry, on 250 DEG C of rotary drum dryers, carbonization is carried out after granulation, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 5:
Be the water glass solution of 3.4 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 5%, add 0.1g Dodecyl trimethyl ammonium chloride, add 5g sorghum starch, 30min is stirred under 90 DEG C of heating, stir speed (S.S.) is 150m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 20% compositions are air) containing 80% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 550 DEG C, temperature out 140 DEG C, atomizing particle size is 25 microns, starch conversion white carbon black finished product is obtained after spraying dry, 220 DEG C of vulcanization beds carry out carbonization, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 6:
Be the water glass solution of 2.6 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 6%, add 0.4g palmityl trimethyl ammonium chloride, add 8g pea starch, 20min is stirred under 95 DEG C of heating, stir speed (S.S.) is 100m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 10% compositions are nitrogen) containing 90% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 400 DEG C, temperature out 100 DEG C, atomizing particle size is 45 microns, starch conversion white carbon black finished product is obtained after spraying dry, on 200 DEG C of vulcanization beds, carbonization is carried out after granulation, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 7:
Be the water glass solution of 3.3 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 13%, add 0.5g tetradecyl trimethyl ammonium chloride, add 6g sweet potato starch and 4g W-Gum, 25min is stirred under 72 DEG C of heating, stir speed (S.S.) is 300m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 25% compositions are air) containing 75% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 250 DEG C, temperature out 80 DEG C, atomizing particle size is 65 microns, starch conversion white carbon black finished product is obtained after spraying dry, 300 DEG C of vulcanization beds carry out carbonization, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 8:
Be the water glass solution of 3.0 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 20%, add 0.6g octadecyl trimethyl ammonium chloride, add 10g glutinous rice starch and 4g tapioca (flour), 30min is stirred under 78 DEG C of heating, stir speed (S.S.) is 250m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 15% compositions are superheated vapour) containing 85% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 650 DEG C, temperature out 105 DEG C, atomizing particle size is 75 microns, starch conversion white carbon black finished product is obtained after spraying dry, 300 DEG C of rotary drum dryers carry out carbonization, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 9:
Be the water glass solution of 3.6 by modulus, adding water and being mixed with 1000g massfraction is 9%, water glass solution, add 0.8g dodecyl tetramethyl ammonium chloride, add 10g sweet potato starch and 8g yam starch, 2g W-Gum, 20min is stirred under 64 DEG C of heating, stir speed (S.S.) is 250m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 90% compositions are air) containing 10% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 700 DEG C, temperature out 140 DEG C, atomizing particle size is 100 microns, starch conversion white carbon black finished product is obtained after spraying dry, on 250 DEG C of rotary drum dryers, carbonization is carried out after granulation, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 10:
Be the water glass solution of 2.9 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 7%, add 0.4g octadecyl tetramethyl ammonium chloride, add 12g tapioca (flour), 20min is stirred under 69 DEG C of heating, stir speed (S.S.) is 50m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 40% compositions are nitrogen) containing 60% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 550 DEG C, temperature out 135 DEG C, atomizing particle size is 85 microns, starch conversion white carbon black finished product is obtained after spraying dry, 280 DEG C of rotary drum dryers carry out carbonization, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 11:
Be the water glass solution of 2.5 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 25%, add 1g tetradecyl tetramethyl ammonium chloride, add 4g W-Gum, 20min is stirred under 74 DEG C of heating, stir speed (S.S.) is 50m/min, pass into after abundant stirring in spray-drying tower, with the gas (air) containing 30% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 620 DEG C, temperature out 115 DEG C, atomizing particle size is 35 microns, starch conversion white carbon black finished product is obtained after spraying dry, 260 DEG C of vulcanization beds carry out carbonization, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 12:
Be the water glass solution of 2.6 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 18%, add 0.6g cetyl tetramethylammonium ammonium chloride, add 14g sorghum starch and 6g glutinous rice starch, 30min is stirred under 88 DEG C of heating, stir speed (S.S.) is 50m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 75% compositions are nitrogen) containing 25% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 440 DEG C, temperature out 115 DEG C, atomizing particle size is 48 microns, starch conversion white carbon black finished product is obtained after spraying dry, on 230 DEG C of vulcanization beds, carbonization is carried out after granulation, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 13:
Be the water glass solution of 3.2 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 23%, add 0.8g tetradecyl 4 bromide, add 16g sweet potato starch, 20min is stirred under 90 DEG C of heating, stir speed (S.S.) is 50m/min, pass into after abundant stirring in spray-drying tower, with the gas (superheated vapour) containing 90% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 280 DEG C, temperature out 95 DEG C, atomizing particle size is 20 microns, starch conversion white carbon black finished product is obtained after spraying dry, on 180 DEG C of rotary drum dryers, carbonization is carried out after granulation, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 14:
Be the water glass solution of 2.8 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 14%, add 0.2g dodecyl 4 bromide, add 9g glutinous rice starch, 25min is stirred under 60 DEG C of heating, stir speed (S.S.) is 50m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 65% compositions are air) containing 35% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 480 DEG C, temperature out 85 DEG C, atomizing particle size is 5 microns, starch conversion white carbon black finished product is obtained after spraying dry, 240 DEG C of rotary drum dryers carry out carbonization, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 15:
Be the water glass solution of 3.4 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 21%, add 0.5g cetyl tetramethylammonium brometo de amonio, add 24g tapioca (flour), 20min is stirred under 75 DEG C of heating, stir speed (S.S.) is 50m/min, pass into after abundant stirring in spray-drying tower, with the gas (other 35% compositions are nitrogen) containing 65% carbonic acid gas, reaction in－situ occurs, spray-drier inlet temperature 525 DEG C, temperature out 105 DEG C, atomizing particle size is 90 microns, starch conversion white carbon black finished product is obtained after spraying dry, on 230 DEG C of rotary drum dryers, carbonization is carried out after granulation, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Embodiment 16:
Be the water glass solution of 3.7 by modulus, add water and be mixed with the water glass solution that 1000g massfraction is 16%, add 0.4g octadecyl 4 bromide, add 14g soybean starch, 20min is stirred under 86 DEG C of heating, stir speed (S.S.) is 50m/min, the gas generation reaction in－situ in spray-drying tower and containing 100% carbonic acid gas is passed into after abundant stirring, spray-drier inlet temperature 250 DEG C, temperature out 70 DEG C, atomizing particle size is 15 microns, starch conversion white carbon black finished product is obtained after spraying dry, 270 DEG C of rotary drum dryers carry out carbonization, novel white carbon black is surveyed its mechanical property by specified mix and compounding rubber after sulfuration.
Comparative example 1:
Goldschmidt chemical corporation produces VN3 type white carbon black, surveys its mechanical property by specified mix and compounding rubber after sulfuration.
In table 1, embodiment and comparative example, glue performance test results filled by white carbon black
In table 2, embodiment and comparative example, glue formula filled by white carbon black
| Material | Mass parts |
| SBR1502 | 100 |
| ZnO | 5 |
| SA | 2 |
| White carbon black | 67 |
| Anti-4020NA | 1 |
| Si69 | 3 |
| CZ | 1.2 |
| S | 1.5 |
Note: the lifting of this modified filler performance is applicable to the various tread glue formula containing butylbenzene, suitable fourth, natural rubber, and embodiment only lists above-mentioned formula with for referencial use.
Claims (4)
1. the preparation method of a white carbon black, it is characterized in that: be 2.4 ~ 3.8 by modulus, mass concentration is the water glass solution of 5% ~ 25%, add the starch of the quaternary ammonium salt of 0.01% ~ 0.1% of water glass solution quality and 2% ~ 25% of water glass solution quality, low whipping speed is 50m/min ~ 300m/min and temperature is under 60 ~ 95 DEG C of conditions, stirring and passing into inlet air temperature after gelatinization is evenly 200 ~ 700 DEG C, temperature out is the gas reaction in－situ in the spray-drying tower of 70 ~ 140 DEG C and containing 10 ~ 100% carbonic acid gas, spraying dry obtains white carbon black finished product, carbonization is carried out at 200 ~ 300 DEG C, or carbonization at 180 ~ 250 DEG C after granulation.
2. the preparation method of a kind of white carbon black according to claim 1, is characterized in that: use quaternary ammonium salt main chain containing carbon number be the quaternary ammonium salt of 12 to 18.
3. the preparation method of a kind of white carbon black according to claim 1, is characterized in that: spray-dired atomizing particle size is 5 ~ 100 microns.
4. the preparation method of a kind of white carbon black according to claim 1, is characterized in that: the starch used is glutinous rice starch, W-Gum, pea starch, tapioca (flour), sweet potato starch, soybean starch, and one or several of sorghum starch are used in combination.
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Application publication date: 20140723 Assignee: ANHUI GURUITE NEW MATERIAL TECHNOLOGY CO.,LTD. Assignor: Anhui Evolutionary Silicon Nanomaterials Technology Co.,Ltd. Contract record no.: X2022980001097 Denomination of invention: A preparation method of silica Granted publication date: 20150805 License type: Common License Record date: 20220126 |