CN103936014A - Preparation method of novel white carbon black - Google Patents
Preparation method of novel white carbon black Download PDFInfo
- Publication number
- CN103936014A CN103936014A CN201410175798.3A CN201410175798A CN103936014A CN 103936014 A CN103936014 A CN 103936014A CN 201410175798 A CN201410175798 A CN 201410175798A CN 103936014 A CN103936014 A CN 103936014A
- Authority
- CN
- China
- Prior art keywords
- carbon black
- white carbon
- starch
- water glass
- spray
- 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.)
- Granted
Links
- 239000006229 carbon black Substances 0.000 title claims abstract description 102
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 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
- 238000003756 stirring Methods 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000011065 in-situ storage Methods 0.000 claims abstract description 24
- 238000001694 spray drying Methods 0.000 claims abstract description 22
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 33
- 235000011089 carbon dioxide Nutrition 0.000 claims description 24
- 238000003763 carbonization Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- 238000005507 spraying Methods 0.000 claims description 21
- 238000005469 granulation Methods 0.000 claims description 10
- 230000003179 granulation Effects 0.000 claims description 10
- 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 26
- 229920001971 elastomer Polymers 0.000 abstract description 24
- 239000005060 rubber Substances 0.000 abstract description 24
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 2
- 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 7
- 230000008569 process Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000000463 material Substances 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
- -1 activated silica alcohol radical Chemical class 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-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
- 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
- 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
- 239000006185 dispersion 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
- 238000007429 general method Methods 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
- AZCDFTXEUCARGI-UHFFFAOYSA-M heptadecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCC[N+](C)(C)C AZCDFTXEUCARGI-UHFFFAOYSA-M 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
- 125000000913 palmityl 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])[H] 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
- 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
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Tires In General (AREA)
Abstract
The invention relates to a preparation method of novel white carbon black. The method comprises the following steps of uniformly stirring a water glass solution with certain modulus as well as quaternary ammonium salt and starch with certain concentration at a certain temperature, reacting with carbon dioxide in situ in a spray-drying tower, spray-drying to obtain finished white carbon black, carbonizing the finished white carbon black at a certain temperature, or granulating and carbonizing. According to the method, the equipment requirement is low, raw materials are simple and easily available, the cost is low, the reaction is quick and efficient, the environment is friendly, and the generated novel white carbon black has unique characteristics, meets the performance indexes of white carbon black for rubber and has relatively good economic benefits.
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 is prepared novel white carbon black, the dry novel white carbon black finished product that directly obtains of spraying, the inventive method is swift in response, and efficiency is high and meet energy-conserving and environment-protective demand.
Background technology
At present, in white carbon black industry, the white carbon black technique of preparing of having realized industry words mainly contains vapor phase process and the precipitator method both at home and abroad.The production method of common domestic high-quality white carbon black is mainly to use vapor phase process, but due to complex process, facility investment is large, and raw material is not easy to obtain, and high in cost of production shortcoming has limited the white carbon black heavy industrialization of high-quality.Although and 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 is hydrated SiO 2, structural formula is SiO2nH2O, has special surface tissue (with surface hydroxyl and planar water), special particle form (particle is little, specific surface area is large etc.) and unique physical and chemical performance.Thereby 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.
At present the white carbon black in the whole world 70%, for rubber industry, is good rubber reinforcing filler, can improve cementing property and tear strength, and its performance is obviously better than ordinary carbon black.
But, due to activated silica alcohol radical and planar water characteristic thereof that poly-silica and the outside surface of traditional white carbon black inside exist, make it be wetting ability, white carbon black is added into after the materials such as rubber, white carbon black is difficult to moistening in organic phase and disperses.And because white carbon black surface exists hydroxyl, surface can be larger, aggregate always tends to cohesion, thereby the application performance of product is affected.
Industrial is often hydrophobicity to the requirement of white carbon black, but contains a large amount of silicon hydroxyls and show very strong wetting ability due to white carbon black surface, therefore improves its interface binding power with polymeric compositions, need 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, eliminate and the amount that reduces surface silicon alcohol radical, make the wetting ability of product change into hydrophobicity, to reach the object of modification.At present, use the most general method of modifying 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 react, react with silicon chlorides etc.But these chemical process raw material costlinesses, complex process, reacts wayward, therefore also defines it and realizes industrialization.
The preparation method of a kind of starch/white carbon black of Chinese patent compounded mix, the white carbon black method of modifying relating to is that white carbon black is sneaked into the blending modification method in the starch paste that gelatinization is in advance good, this method technique is simple, be easy to realize, but be only the modification to white carbon black finished product, being coated as simple absorption between starch and white carbon black.
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 shape and props up two kinds of chains, and it is a kind of strong polyhydric crystal material of polarity.On 2,3,6 carbon in each glucose structural unit of starch molecule, contain hydroxyl, have these to there is chemically active hydroxyl, thus can with chemical compound lot generation grafting, crosslinking reaction, this makes that starch is carried out to modification 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, make 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 spray-drying tower, pass into the water glass solution and the carbon dioxide reaction that contain starch and prepare novel white carbon black, the dry coated white carbon black finished product of starch that obtains of spraying.The problems such as such method has fundamentally solved white carbon black easily reunites, difficult dispersion.Adopt carbonic acid gas to be dried the technique of direct in-situ generation novel white carbon black by spraying with the water glass solution that contains starch, 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 5%～25% water glass solution, adds 2%～25% starch of 0.01%～0.1% quaternary ammonium salt of water glass solution quality and water glass solution quality, and low whipping speed is
50m/min～300m/min and temperature are under 60～95 DEG C of conditions, after stirring is even with gelatinization, passing into inlet air temperature is 200～700 DEG C, temperature out be in the spray-drying tower of 70～140 DEG C with the gas reaction in－situ that contains 10～100% carbonic acid gas, the dry novel white carbon black finished product that obtains of spraying, at 200～300 DEG C, carry out carbonization, 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, starch consumption is 2%～25% of water glass quality.
As preferably: the quaternary ammonium salt using for main chain be 12 to 18 quaternary ammonium salt 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 quaternary ammonium salt is fully dissolved and is dispersed in water glass solution, make at a certain temperature the abundant gelatinization of starch in water glass solution.Amyloid water glass good gelatinization is passed in the spray-drying tower of certain temperature, under the effect of atomizing disk high speed centrifugation, be atomized into a large amount of fine mist, particle diameter is 5～100 microns, amyloid water glass solution is under the effect of quaternary ammonium salt, starch and water glass in droplet 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 that contains 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 equably white carbon black surface, reduce white carbon black hydroxy radical content, some characteristics of starch have been introduced simultaneously, thereby form the white carbon black that is coated with one deck new texture, finally white carbon black coated starch is carried out to carbonization after carbonization or granulation, thereby make this white carbon black have more characteristics.
After carbonization, containing the novel white carbon black of carbon structure, have 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 a 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, has greatly improved 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) solved white carbon black easy problem such as reunion, airborne dust in polymkeric substance.
(7) novel white carbon black has unique characteristic.
Embodiment
Embodiment 1:
The water glass solution that is 3.8 by modulus, adding water and being mixed with 1000g massfraction is 10% water glass solution, add 0.2g Trimethyllaurylammonium bromide, add 2g glutinous rice starch, under 70 DEG C of heating, stir 30min, stir speed (S.S.) is 100m/min, after fully stirring, pass in spray-drying tower, with the gas (other 50% compositions are air) that contains 50% carbonic acid gas, reaction in－situ occurs, 300 DEG C of spray-drier inlet temperatures, 90 DEG C of temperature outs, atomizing particle size is 5 microns, after spraying is dry, obtain starch conversion white carbon black finished product and carry out carbonization on 200 DEG C of vulcanization beds, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 2:
The water glass solution that is 2.4 by modulus, adding water and being mixed with 1000g massfraction is 15% water glass solution, add 0.5g Tetradecyl Trimethyl Ammonium Bromide, add 10g W-Gum, under 68 DEG C of heating, stir 30min, stir speed (S.S.) is 150m/min, fully stir to pass in spray-drying tower, with the gas (other 80% compositions are nitrogen) that contains 20% carbonic acid gas, reaction in－situ occurs, 200 DEG C of spray-drier inlet temperatures, 70 DEG C of temperature outs, atomizing particle size is 10 microns, after spraying is dry, obtain starch conversion white carbon black finished product, after granulation, on 180 DEG C of vulcanization beds, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 3:
The water glass solution that is 2.8 by modulus, adding water and being mixed with 1000g massfraction is 22% water glass solution, add 1g cetyl trimethylammonium bromide, add 25g tapioca (flour), under 85 DEG C of heating, stir 30min, stir speed (S.S.) is 180m/min, after fully stirring, passes in spray-drying tower, with the gas (other 60% compositions are air) that contains 40% carbonic acid gas, reaction in－situ occurs
500 DEG C of spray-drier inlet temperatures, 120 DEG C of temperature outs, atomizing particle size is 30 microns, after spraying is dry, obtains starch conversion white carbon black finished product, on 200 DEG C of rotary drum dryers, carry out carbonization, novel white carbon black is pressed to rear its mechanical property of surveying of specified mix and compounding rubber sulfuration.
Embodiment 4:
The water glass solution that is 3.1 by modulus, adding water and being mixed with 1000g massfraction is 8% water glass solution, add 0.4g Cetyltrimethylammonium bromide, add 15g soybean starch, under 80 DEG C of heating, stir 20min, stir speed (S.S.) is 200m/min, after fully stirring, pass in spray-drying tower, with the gas (other 30% compositions are superheated vapour) that contains 70% carbonic acid gas, reaction in－situ occurs, 600 DEG C of spray-drier inlet temperatures, 110 DEG C of temperature outs, atomizing particle size is 50 microns, after spraying is dry, obtain starch conversion white carbon black finished product, after granulation, on 250 DEG C of rotary drum dryers, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 5:
The water glass solution that is 3.4 by modulus, adding water and being mixed with 1000g massfraction is 5% water glass solution, add 0.1g Dodecyl trimethyl ammonium chloride, add 5g sorghum starch, under 90 DEG C of heating, stir 30min, stir speed (S.S.) is 150m/min, after fully stirring, pass in spray-drying tower, with the gas (other 20% compositions are air) that contains 80% carbonic acid gas, reaction in－situ occurs, 550 DEG C of spray-drier inlet temperatures, 140 DEG C of temperature outs, atomizing particle size is 25 microns, after spraying is dry, obtain starch conversion white carbon black finished product, on 220 DEG C of vulcanization beds, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 6:
The water glass solution that is 2.6 by modulus, adding water and being mixed with 1000g massfraction is 6% water glass solution, add 0.4g palmityl trimethyl ammonium chloride, add 8g pea starch, under 95 DEG C of heating, stir 20min, stir speed (S.S.) is 100m/min, after fully stirring, pass in spray-drying tower, with the gas (other 10% compositions are nitrogen) that contains 90% carbonic acid gas, reaction in－situ occurs, 400 DEG C of spray-drier inlet temperatures, 100 DEG C of temperature outs, atomizing particle size is 45 microns, after spraying is dry, obtain starch conversion white carbon black finished product, after granulation, on 200 DEG C of vulcanization beds, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 7:
The water glass solution that is 3.3 by modulus, adding water and being mixed with 1000g massfraction is 13% water glass solution, add 0.5g tetradecyl trimethyl ammonium chloride, add 6g sweet potato starch and 4g W-Gum, under 72 DEG C of heating, stir 25min, stir speed (S.S.) is 300m/min, after fully stirring, pass in spray-drying tower, with the gas (other 25% compositions are air) that contains 75% carbonic acid gas, reaction in－situ occurs, 250 DEG C of spray-drier inlet temperatures, 80 DEG C of temperature outs, atomizing particle size is 65 microns, after spraying is dry, obtain starch conversion white carbon black finished product, on 300 DEG C of vulcanization beds, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 8:
The water glass solution that is 3.0 by modulus, adding water and being mixed with 1000g massfraction is 20% water glass solution, add 0.6g octadecyl trimethyl ammonium chloride, add 10g glutinous rice starch and 4g tapioca (flour), under 78 DEG C of heating, stir 30min, stir speed (S.S.) is 250m/min, after fully stirring, pass in spray-drying tower, with the gas (other 15% compositions are superheated vapour) that contains 85% carbonic acid gas, reaction in－situ occurs, 650 DEG C of spray-drier inlet temperatures, 105 DEG C of temperature outs, atomizing particle size is 75 microns, after spraying is dry, obtain starch conversion white carbon black finished product, on 300 DEG C of rotary drum dryers, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 9:
The water glass solution that is 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, under 64 DEG C of heating, stir 20min, stir speed (S.S.) is 250m/min, after fully stirring, pass in spray-drying tower, with the gas (other 90% compositions are air) that contains 10% carbonic acid gas, reaction in－situ occurs, 700 DEG C of spray-drier inlet temperatures, 140 DEG C of temperature outs, atomizing particle size is 100 microns, after spraying is dry, obtain starch conversion white carbon black finished product, after granulation, on 250 DEG C of rotary drum dryers, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 10:
The water glass solution that is 2.9 by modulus, adding water and being mixed with 1000g massfraction is 7% water glass solution, add 0.4g octadecyl tetramethyl ammonium chloride, add 12g tapioca (flour), under 69 DEG C of heating, stir 20min, stir speed (S.S.) is 50m/min, after fully stirring, pass in spray-drying tower, with the gas (other 40% compositions are nitrogen) that contains 60% carbonic acid gas, reaction in－situ occurs, 550 DEG C of spray-drier inlet temperatures, 135 DEG C of temperature outs, atomizing particle size is 85 microns, after spraying is dry, obtain starch conversion white carbon black finished product, on 280 DEG C of rotary drum dryers, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 11:
The water glass solution that is 2.5 by modulus, adding water and being mixed with 1000g massfraction is 25% water glass solution, add 1g tetradecyl tetramethyl ammonium chloride, add 4g W-Gum, under 74 DEG C of heating, stir 20min, stir speed (S.S.) is 50m/min, after fully stirring, pass in spray-drying tower, with the gas (air) that contains 30% carbonic acid gas, reaction in－situ occurs, 620 DEG C of spray-drier inlet temperatures, 115 DEG C of temperature outs, atomizing particle size is 35 microns, after spraying is dry, obtain starch conversion white carbon black finished product, on 260 DEG C of vulcanization beds, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 12:
The water glass solution that is 2.6 by modulus, adding water and being mixed with 1000g massfraction is 18% water glass solution, add 0.6g hexadecyl tetramethyl ammonium chloride, add 14g sorghum starch and 6g glutinous rice starch, under 88 DEG C of heating, stir 30min, stir speed (S.S.) is 50m/min, after fully stirring, pass in spray-drying tower, with the gas (other 75% compositions are nitrogen) that contains 25% carbonic acid gas, reaction in－situ occurs, 440 DEG C of spray-drier inlet temperatures, 115 DEG C of temperature outs, atomizing particle size is 48 microns, after spraying is dry, obtain starch conversion white carbon black finished product, after granulation, on 230 DEG C of vulcanization beds, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.Embodiment 13:
The water glass solution that is 3.2 by modulus, adding water and being mixed with 1000g massfraction is 23% water glass solution, add 0.8g tetradecyl 4 bromide, add 16g sweet potato starch, under 90 DEG C of heating, stir 20min, stir speed (S.S.) is 50m/min, after fully stirring, pass in spray-drying tower, with the gas (superheated vapour) that contains 90% carbonic acid gas, reaction in－situ occurs, 280 DEG C of spray-drier inlet temperatures, 95 DEG C of temperature outs, atomizing particle size is 20 microns, after spraying is dry, obtain starch conversion white carbon black finished product, after granulation, on 180 DEG C of rotary drum dryers, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 14:
The water glass solution that is 2.8 by modulus, adding water and being mixed with 1000g massfraction is 14% water glass solution, add 0.2g dodecyl 4 bromide, add 9g glutinous rice starch, under 60 DEG C of heating, stir 25min, stir speed (S.S.) is 50m/min, after fully stirring, pass in spray-drying tower, with the gas (other 65% compositions are air) that contains 35% carbonic acid gas, reaction in－situ occurs, 480 DEG C of spray-drier inlet temperatures, 85 DEG C of temperature outs, atomizing particle size is 5 microns, after spraying is dry, obtain starch conversion white carbon black finished product, on 240 DEG C of rotary drum dryers, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 15:
The water glass solution that is 3.4 by modulus, adding water and being mixed with 1000g massfraction is 21% water glass solution, add 0.5g hexadecyl 4 bromide, add 24g tapioca (flour), under 75 DEG C of heating, stir 20min, stir speed (S.S.) is 50m/min, after fully stirring, pass in spray-drying tower, with the gas (other 35% compositions are nitrogen) that contains 65% carbonic acid gas, reaction in－situ occurs, 525 DEG C of spray-drier inlet temperatures, 105 DEG C of temperature outs, atomizing particle size is 90 microns, after spraying is dry, obtain starch conversion white carbon black finished product, after granulation, on 230 DEG C of rotary drum dryers, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Embodiment 16:
The water glass solution that is 3.7 by modulus, adding water and being mixed with 1000g massfraction is 16% water glass solution, add 0.4g octadecyl 4 bromide, add 14g soybean starch, under 86 DEG C of heating, stir 20min, stir speed (S.S.) is 50m/min, the gas generation reaction in－situ that passes in spray-drying tower and contain 100% carbonic acid gas after fully stirring, 250 DEG C of spray-drier inlet temperatures, 70 DEG C of temperature outs, atomizing particle size is 15 microns, after spraying is dry, obtain starch conversion white carbon black finished product, on 270 DEG C of rotary drum dryers, carry out carbonization, after being pressed to specified mix and compounding rubber sulfuration, novel white carbon black surveys its mechanical property.
Comparative example 1:
Goldschmidt chemical corporation is produced VN3 type white carbon black, by surveying its mechanical property after specified mix and compounding rubber sulfuration.
In table 1, embodiment and comparative example, white carbon black is filled glue performance test results
In table 2, embodiment and comparative example, white carbon black is filled glue formula
| 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 various containing butylbenzene, along the tread glue formula of 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 5%～25% water glass solution, add 2%～25% starch of 0.01%～0.1% quaternary ammonium salt of water glass solution quality and water glass solution quality, low whipping speed is that 50m/min～300m/min and temperature are under 60～95 DEG C of conditions, after stirring is even with gelatinization, passing into inlet air temperature is 200～700 DEG C, temperature out be in the spray-drying tower of 70～140 DEG C with the gas reaction in－situ that contains 10～100% carbonic acid gas, the dry novel white carbon black finished product that obtains of spraying, at 200～300 DEG C, carry out carbonization, 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: the quaternary ammonium salt main chain that uses be 12 to 18 quaternary ammonium salt containing carbon number.
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 using is glutinous rice starch, W-Gum, and pea starch, tapioca (flour), sweet potato starch, soybean starch, one or several of sorghum starch mix use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410175798.3A CN103936014B (en) | 2014-04-28 | 2014-04-28 | A kind of preparation method of white carbon black |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410175798.3A CN103936014B (en) | 2014-04-28 | 2014-04-28 | A kind of preparation method of white carbon black |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103936014A true CN103936014A (en) | 2014-07-23 |
| CN103936014B CN103936014B (en) | 2015-08-05 |
Family
ID=51183941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410175798.3A Active CN103936014B (en) | 2014-04-28 | 2014-04-28 | A kind of preparation method of white carbon black |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103936014B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105997582A (en) * | 2016-05-20 | 2016-10-12 | 林中 | Special filler for plant carbon black coloring cosmetics and preparation method thereof |
| CN110193890A (en) * | 2019-06-06 | 2019-09-03 | 益凯新材料有限公司 | A kind of wet process mixing continuous production technology of isoprene rubber |
| CN111960428A (en) * | 2020-09-04 | 2020-11-20 | 桂林良物造日用品有限公司 | Modification method of nano white carbon black |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112991A (en) * | 2006-07-24 | 2008-01-30 | 北京化工大学 | Method for preparing silicon dioxide with large pore volume and large aperture |
| CN103387696A (en) * | 2013-07-29 | 2013-11-13 | 海南大学 | In-situ polymerization method of nano starch/SiO2 composite particles |
-
2014
- 2014-04-28 CN CN201410175798.3A patent/CN103936014B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112991A (en) * | 2006-07-24 | 2008-01-30 | 北京化工大学 | Method for preparing silicon dioxide with large pore volume and large aperture |
| CN103387696A (en) * | 2013-07-29 | 2013-11-13 | 海南大学 | In-situ polymerization method of nano starch/SiO2 composite particles |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105997582A (en) * | 2016-05-20 | 2016-10-12 | 林中 | Special filler for plant carbon black coloring cosmetics and preparation method thereof |
| CN110193890A (en) * | 2019-06-06 | 2019-09-03 | 益凯新材料有限公司 | A kind of wet process mixing continuous production technology of isoprene rubber |
| CN111960428A (en) * | 2020-09-04 | 2020-11-20 | 桂林良物造日用品有限公司 | Modification method of nano white carbon black |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103936014B (en) | 2015-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tronc et al. | Blue agave fiber esterification for the reinforcement of thermoplastic composites | |
| CN103937293B (en) | A kind of carbon cladding white carbon | |
| CN103387757B (en) | A kind of preparation method of overcritical middle hydrotalcite grafting fire retardant | |
| CN103316639B (en) | Preparation method of organic modified sepiolite adsorbent | |
| CN110093680B (en) | Graphene/cage type polysilsesquioxane modified polyester fiber and preparation method thereof | |
| CN101880478A (en) | Method for preparing hydrophobic nano-silica with controllable grain diameter | |
| CN109943902B (en) | Modified polyester fiber and preparation method thereof | |
| CN104087027B (en) | A kind of heat resist modification calcium carbonate and preparation method thereof | |
| CN103627055B (en) | Utilize the method that modified microcrystalline cellulose prepares tire tread glue | |
| CN103936014B (en) | A kind of preparation method of white carbon black | |
| CN108623833A (en) | A kind of preparation method of multi-functional aerogel composite | |
| CN109749108A (en) | A kind of edible tapioca composite package film and its preparation method and application | |
| CN102031025A (en) | Method for preparing silicone oil surface modified aluminium hydroxide flame retardant | |
| CN106589390A (en) | Modification method for hydrophobic grafting of nano-cellulose crystal | |
| CN111877008A (en) | Highly breathable superhydrophobic fibers | |
| CN103936013B (en) | A kind of method preparing white carbon black slurries | |
| CN110511434A (en) | A kind of preparation method and applications for mixing silver-colored halloysite nanotubes composite material of the cladding containing polyphosphazene | |
| CN103466643A (en) | Method for preparing white carbon black by circularly using mother liquor | |
| CN108912555A (en) | A kind of preparation method of high-weatherability PVC wallboard | |
| CN112280260A (en) | High-barrier PLA/PBAT composite packaging film | |
| CN109535770B (en) | Functionalized graphene oxide and preparation method and application thereof | |
| CN104650303B (en) | Preparation method of modified oil-extended high-performance powdered styrene-butadiene rubber | |
| CN108192142B (en) | Modification method of high-dispersion carbon nano tube used as rubber filler | |
| CN109233064A (en) | A kind of composite polyethylene solid wall pipe and preparation method thereof | |
| CN103483651B (en) | A kind of nanometer SSBR rubber processing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Yiqing Inventor after: Shen Jiafeng Inventor after: Wang Hong Inventor after: Deng Siqi Inventor after: Zhang Liqun Inventor before: Wang Yiqing Inventor before: Shen Jiafeng Inventor before: Deng Siqi Inventor before: Zhang Liqun |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: WANG YIQING SHEN JIAFENG DENG SIQI ZHANG LIQUN TO: WANG YIQING SHEN JIAFENG WANG HONG DENG SIQI ZHANG LIQUN |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20181212 Address after: 236400 Room 518 Xin'an Road, Jingjiu Office, Fuyang Development Zone, Anhui Province Patentee after: Anhui Evolutionary Silicon Nanomaterials Technology Co., Ltd. Address before: 100029, No. 15 East Third Ring Road, Chaoyang District, Beijing Patentee before: Beijing University of Chemical Technology |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
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 |