CN105271250B - A kind of method for preparing modified white carbon black - Google Patents
A kind of method for preparing modified white carbon black Download PDFInfo
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- CN105271250B CN105271250B CN201510692570.6A CN201510692570A CN105271250B CN 105271250 B CN105271250 B CN 105271250B CN 201510692570 A CN201510692570 A CN 201510692570A CN 105271250 B CN105271250 B CN 105271250B
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Abstract
The invention discloses a kind of methods for preparing modified white carbon black, belong to white carbon technical field of modification.Modified white carbon black of the present invention is using granite as raw material; impurity is removed by immersions such as sodium hydroxide solutions; raw material are carried out simultaneously tentatively modified; under the protection of mixed gas, preliminary modified white carbon black is prepared, then by adding in the substances such as ammonium hydrogen carbonate, fatty alcohol polyoxyethylene ether; high temperature, ultraviolet lamp irradiation under; modified white carbon black crude product is generated, it is dry to be made finally through washing.The beneficial effects of the invention are as follows：Environmentally safe without using a large amount of organic solvents in production process of the present invention, modification is at low cost；Products obtained therefrom post-processing is simple, and treatment effect is apparent, modified uniform, has the characteristics that ageing-resistant performance is good, compression set is low and high stretches performance surely.
Description
Technical field
The present invention relates to a kind of methods for preparing modified white carbon black, belong to white carbon technical field of modification.
Background technology
White carbon is the general name of white powder X-ray amorphous silicic acid and silicate product, is primarily referred to as precipitation dioxy
SiClx, aerosil and superfine silicon dioxide gel, also including powdered synthetic aluminium silicate and calcium silicates etc..White carbon is
Porous material, composition can represent that wherein nH2O is existed in the form of surface hydroxyl with SiO2nH2O.Causticity can be dissolved in
Alkali and hydrofluoric acid, not soluble in water, solvent and acid（Except hydrofluoric acid）.High temperature resistant, it is non-ignitable, tasteless, odorless, have well electricity absolutely
Edge.Due to activated silica alcohol radical existing for the poly- silica inside white carbon and outer surface and its absorption water, it is in hydrophily to make it,
It is difficult to moisten and disperse in organic phase, moreover, because its surface, there are hydroxyl, surface can be larger, and aggregation always tends to agglomerate,
Thus the application performance of product is affected.Such as in vulcanization of rubber system, unmodified white carbon cannot polymerize well
Disperse in object, coupling key is hardly formed between filler, polymer, so as to reduce curing efficiency and reinforcing property.The table of white carbon
It is that the surface hydroxyl of white carbon and chemical substance occurs by certain process using certain chemical substance that face, which is modified,
Reaction, eliminates or reduces the amount of its surface-active silanol group, product is made to become hydrophobic from hydrophilic, increases its point in the polymer
Dissipate property.
At present there are mainly three types of the method for modifying of white carbon, i.e. dry method modification, wet-process modified and hot pressing is modified.It is wet-process modified
Few with amount of modifier, modification is at low cost, but because a large amount of organic solvents is used to cause product post-processing complicated, easily causes ring
It pollutes in border.Dry method modification avoid it is wet-process modified using organic solvent the shortcomings that, have simple for process, treating capacity is big, rear to locate
Reason is simple, and reaction efficiency is high, but operating condition is stringent, and amount of modifier is big, and modification is of high cost, modified non-uniform shortcoming.
And there are high energy consumptions for pressure sintering modification, equipment requirement is high, and treating capacity is relatively small, and amount of modifier is big, modified non-uniform scarce
Point.
Invention content
The technical problems to be solved by the invention：It is needed in the process using a large amount of organic solvent, dry method for wet-process modified
Amount of modifier is big in modifying process, and the requirement of pressure sintering modified device is high, and treating capacity is smaller, causes product post-processing complicated,
It pollutes the environment, modified of high cost, high energy consumption, modified non-uniform drawback, provides a kind of modified white carbon black for preparing
Method, the present invention removes impurity using granite as raw material, by immersions such as sodium hydroxide solutions, while raw material is carried out preliminary
It is modified, under the protection of mixed gas, preliminary modified white carbon black is prepared, then by adding in ammonium hydrogen carbonate, fatty alcohol polyoxy second
The substances such as alkene ether, high temperature, ultraviolet lamp irradiation under, generate modified white carbon black crude product, finally through washing, be dried to obtain modified white
Carbon black.Products obtained therefrom chemism is good, and production cost is low, and modified uniform, environmentally safe, low energy consumption.
In order to solve the above technical problems, the present invention is using technical solution as described below：
（1）1~3g granite is taken to be put into building stones flour mill to crush, be sieved to obtain 80~100 mesh particles, by gained
Particle is put into container, is added in the sodium hydroxide solution that mass fraction is 60% thereto and is flooded 2~4cm of particulate matter, stirring 30
~40min, then after standing 1~2h, filter to obtain filtrate；
（2）The above-mentioned filtrates of 400~600g are weighed to be put into 50L reaction kettles, add in thereto mass concentration for 70~
75% sulfuric acid solution floods 4~6cm of filtrate, and reaction kettle is carried out using mixed gas to be forced into 1~2MPa, the mixing
Gas is fluorine gas, nitrogen and oxygen by volume 1:5:2 mix, and are slowly stirred and are warming up to 60~70 DEG C, and heating rate is
10 DEG C/h, rotating speed is set as 110~120r/min；
（3）When the pH of mixture in aforesaid reaction vessel is 6.5~7.0, it being decompressed to standard atmospheric pressure, temperature is reduced to 28~
It 35 DEG C, discharges after standing 4~8h, the material that goes out of gained is put into centrifuge and is centrifuged, centrifugation object is obtained, by gained
It centrifuges object and presses solid-to-liquid ratio 1 with water:3, which carry out mixing, is put into container, and then temperature in use is 200~230 DEG C of superheated steam pair
It heats 20~30min；
（4）After treating above-mentioned heating, be separately added into thereto 100~200mL fatty alcohol polyoxyethylene ether, 160~
190g ammonium hydrogen carbonate and 10~20g isobutyl triethoxy silanes stir evenly, and then add in 300~400mL positive third thereto
Alcohol is 120~160 DEG C in temperature, and frequency is under the ultrasonic wave of 25~30kHz, stirs 3~7h, and matter is used in whipping process
The sodium hydroxide solution that amount score is 45% ensures that its pH is 6.5~7.5；
（5）It treats to filter after above-mentioned stirring, filtrate is rinsed 2~4 times using deionized water, is then pressed with water
According to solid-to-liquid ratio 1:5, under 1000~1200r/min of rotating speed, after stirring 10~15min, white carbon slurry is obtained, by the hard charcoal of gained
Black wash material obtains modified white carbon black after centrifugal spray drying.
The modified white carbon black fusing point of the present invention is 1490~1580 DEG C, and chemism is good, and reinforcing effect is good, density 2.8
~3.0g/mL, ageing-resistant performance is good, compression set is low and high stretches performance surely.
Compared with other methods, advantageous effects are the present invention：
（1）Environmentally safe without using a large amount of organic solvents in production process of the present invention, modification is at low cost；
（2）Products obtained therefrom post-processing is simple, and treatment effect is apparent, modified uniform, have ageing-resistant performance is good, compression forever
Low and high the features such as stretching performance surely is deformed long.
Specific embodiment
1~3g granite is taken to be put into building stones flour mill first to crush, be sieved to obtain 80~100 mesh particles, by gained
Particle be put into container, thereto add in mass fraction be 60% sodium hydroxide solution flood 2~4cm of particulate matter, stir
30~40min, then after standing 1~2h, filter to obtain filtrate；The above-mentioned filtrates of 400~600g are weighed again is put into 50L reaction kettles
In, the sulfuric acid solution that mass concentration is 70~75% is added in thereto and floods 4~6cm of filtrate, using mixed gas to reaction
Kettle be forced into 1~2MPa, and the mixed gas is fluorine gas, nitrogen and oxygen by volume 1:5:2 mix, and slowly stir
It mixes and is warming up to 60~70 DEG C, heating rate is 10 DEG C/h, and rotating speed is set as 110~120r/min；It treats to mix in aforesaid reaction vessel
When the pH of object is 6.5~7.0, standard atmospheric pressure is decompressed to, temperature is reduced to 28~35 DEG C, discharges after standing 4~8h, by gained
Go out material and be put into centrifuge to be centrifuged, obtain centrifugation object, the centrifugation object of gained and water are pressed into solid-to-liquid ratio 1:3 are mixed
It is put into container, then temperature in use is that 200~230 DEG C of superheated steam heats 20~30min to it；Then above-mentioned heating is treated
After, it is different that it is separately added into 100~200mL fatty alcohol polyoxyethylene ether, 160~190g ammonium hydrogen carbonate and 10~20g thereto
Butyl triethoxysilane stirs evenly, and then adds in 300~400mL normal propyl alcohols thereto, is 120~160 DEG C in temperature, frequency
Rate is under the ultrasonic wave of 25~30kHz, stirs 3~7h, and the sodium hydroxide that use quality score is 45% in whipping process is molten
Liquid ensures that its pH is 6.5~7.5；It finally treats to filter after above-mentioned stirring, it is rinsed 2 to filtrate using deionized water~
4 times, then with water according to solid-to-liquid ratio 1:5, under 1000~1200r/min of rotating speed, after stirring 10~15min, obtain hard charcoal black wash
Material, by the white carbon slurry of gained after centrifugal spray drying, obtains modified white carbon black.
Example 1
1g granite is taken to be put into building stones flour mill first to crush, be sieved to obtain 80 mesh particles, and the particle of gained is put
Enter in container, add in the sodium hydroxide solution that mass fraction is 60% thereto and flood particulate matter 2cm, stir 30min, then stand
After 1h, filtrate is filtered to obtain；It weighs the above-mentioned filtrates of 400g again to be put into 50L reaction kettles, adding in mass concentration thereto is
70% sulfuric acid solution floods filtrate 4cm, reaction kettle is carried out using mixed gas to be forced into 1MPa, the mixed gas is
Fluorine gas, nitrogen and oxygen by volume 1:5:2 mix, and are slowly stirred and are warming up to 60 DEG C, and heating rate is 10 DEG C/h, rotating speed
It is set as 110r/min；When the pH of mixture in aforesaid reaction vessel is 6.5, standard atmospheric pressure is decompressed to, temperature is reduced to 28 DEG C,
Discharge after standing 4h, the material that goes out of gained be put into centrifuge and is centrifuged, obtains centrifugation object, by the centrifugation object of gained with
Water presses solid-to-liquid ratio 1:3, which carry out mixing, is put into container, and then temperature in use is that 200 DEG C of superheated steam heats 20min to it；So
After treat above-mentioned heating after, be separately added into 100mL fatty alcohol polyoxyethylene ether, 160g ammonium hydrogen carbonate and 10g isobutyls thereto
Ethyl triethoxy silicane alkane stirs evenly, and then adds in 300mL normal propyl alcohols thereto, is 120 DEG C in temperature, frequency is 25kHz's
Under ultrasonic wave, 3h is stirred, the sodium hydroxide solution that use quality score is 45% in whipping process ensures that its pH is 6.5；Most
After treat to filter after above-mentioned stirring, filtrate is rinsed 2 times using deionized water, then with water according to solid-to-liquid ratio 1:5,
Under rotating speed 1000r/min, after stirring 10min, white carbon slurry is obtained, by the white carbon slurry of gained through centrifugal spray drying
Afterwards, modified white carbon black is obtained.
The modified white carbon black fusing point of the present invention is 1490 DEG C, and chemism is good, and reinforcing effect is good, density 3.0g/mL, raw
Environmentally safe without using a large amount of organic solvents during production, modification is at low cost；Products obtained therefrom post-processing is simple, place
Manage it is with obvious effects, it is modified uniform, have the characteristics that ageing-resistant performance is good, compression set is low and high stretch performance surely.
Example 2
2g granite is taken to be put into building stones flour mill first to crush, be sieved to obtain 90 mesh particles, and the particle of gained is put
Enter in container, add in the sodium hydroxide solution that mass fraction is 60% thereto and flood particulate matter 3cm, stir 35min, then stand
After 1.5h, filtrate is filtered to obtain；It weighs the above-mentioned filtrates of 500g again to be put into 50L reaction kettles, adding in mass concentration thereto is
73% sulfuric acid solution floods filtrate 5cm, and reaction kettle is carried out using mixed gas to be forced into 1.5MPa, the mixed gas
For fluorine gas, nitrogen and oxygen by volume 1:5:2 mix, and are slowly stirred and are warming up to 65 DEG C, heating rate is 10 DEG C/h, is turned
Speed is set as 115r/min；When the pH of mixture in aforesaid reaction vessel is 6.8, standard atmospheric pressure is decompressed to, temperature is reduced to 32
DEG C, it discharges after standing 6h, the material that goes out of gained is put into centrifuge and is centrifuged, centrifugation object is obtained, by the centrifugation of gained
Object presses solid-to-liquid ratio 1 with water:3, which carry out mixing, is put into container, and then temperature in use is that 215 DEG C of superheated steam heats it
25min；Then after treating above-mentioned heating, be separately added into thereto 150mL fatty alcohol polyoxyethylene ether, 175g ammonium hydrogen carbonate and
15g isobutyl triethoxy silanes stir evenly, and then add in 350mL normal propyl alcohols thereto, are 140 DEG C in temperature, frequency is
Under the ultrasonic wave of 28kHz, 5h is stirred, the sodium hydroxide solution that use quality score is 45% in whipping process ensures that its pH is
7.0；It finally treats to filter after above-mentioned stirring, filtrate is rinsed 3 times using deionized water, then with water according to solid-liquid
Than 1:5, under rotating speed 1100r/min, after stirring 12min, white carbon slurry is obtained, by the white carbon slurry of gained through centrifugal spray
After drying, modified white carbon black is obtained.
The modified white carbon black fusing point of the present invention is 1540 DEG C, and chemism is good, and reinforcing effect is good, density 2.9g/mL, raw
Environmentally safe without using a large amount of organic solvents during production, modification is at low cost；Products obtained therefrom post-processing is simple, place
Manage it is with obvious effects, it is modified uniform, have the characteristics that ageing-resistant performance is good, compression set is low and high stretch performance surely.
Example 3
3g granite is taken to be put into building stones flour mill first to crush, be sieved to obtain 100 mesh particles, and the particle of gained is put
Enter in container, add in the sodium hydroxide solution that mass fraction is 60% thereto and flood particulate matter 4cm, stir 40min, then stand
After 2h, filtrate is filtered to obtain；It weighs the above-mentioned filtrates of 600g again to be put into 50L reaction kettles, adding in mass concentration thereto is
75% sulfuric acid solution floods filtrate 6cm, reaction kettle is carried out using mixed gas to be forced into 2MPa, the mixed gas is
Fluorine gas, nitrogen and oxygen by volume 1:5:2 mix, and are slowly stirred and are warming up to 70 DEG C, and heating rate is 10 DEG C/h, rotating speed
It is set as 120r/min；When the pH of mixture in aforesaid reaction vessel is 7.0, standard atmospheric pressure is decompressed to, temperature is reduced to 35 DEG C,
Discharge after standing 8h, the material that goes out of gained be put into centrifuge and is centrifuged, obtains centrifugation object, by the centrifugation object of gained with
Water presses solid-to-liquid ratio 1:3, which carry out mixing, is put into container, and then temperature in use is that 230 DEG C of superheated steam heats 30min to it；So
After treat above-mentioned heating after, be separately added into 200mL fatty alcohol polyoxyethylene ether, 190g ammonium hydrogen carbonate and 20g isobutyls thereto
Ethyl triethoxy silicane alkane stirs evenly, and then adds in 400mL normal propyl alcohols thereto, is 160 DEG C in temperature, frequency is 30kHz's
Under ultrasonic wave, 7h is stirred, the sodium hydroxide solution that use quality score is 45% in whipping process ensures that its pH is 7.5；Most
After treat to filter after above-mentioned stirring, filtrate is rinsed 4 times using deionized water, then with water according to solid-to-liquid ratio 1:5,
Under rotating speed 1200r/min, after stirring 15min, white carbon slurry is obtained, by the white carbon slurry of gained through centrifugal spray drying
Afterwards, modified white carbon black is obtained.
The modified white carbon black fusing point of the present invention is 1580 DEG C, and chemism is good, and reinforcing effect is good, density 3.0g/mL, raw
Environmentally safe without using a large amount of organic solvents during production, modification is at low cost；Products obtained therefrom post-processing is simple, place
Manage it is with obvious effects, it is modified uniform, have the characteristics that ageing-resistant performance is good, compression set is low and high stretch performance surely.
Claims (1)
- A kind of 1. method for preparing modified white carbon black, it is characterised in that specifically preparation process is：（1）1~3g granite is taken to be put into building stones flour mill to crush, be sieved to obtain 80~100 mesh particles, by the particle of gained It is put into container, adds in the sodium hydroxide solution that mass fraction is 60% thereto and flood 2~4cm of particulate matter, stirring 30~ 40min, then after standing 1~2h, filter to obtain filtrate；（2）It weighs the above-mentioned filtrates of 400~600g to be put into 50L reaction kettles, it is 70~75% to add in mass concentration thereto Sulfuric acid solution floods 4~6cm of filtrate, reaction kettle is carried out using mixed gas to be forced into 1~2MPa, the mixed gas is Fluorine gas, nitrogen and oxygen by volume 1:5:2 mix, and are slowly stirred and are warming up to 60~70 DEG C, and heating rate is 10 DEG C/h, Rotating speed is set as 110~120r/min；（3）When the pH of mixture in aforesaid reaction vessel is 6.5~7.0, standard atmospheric pressure is decompressed to, temperature is reduced to 28~35 DEG C, discharge after standing 4~8h, the material that goes out of gained be put into centrifuge and is centrifuged, obtains centrifugation object, by gained from Heart object presses solid-to-liquid ratio 1 with water:3, which carry out mixing, is put into container, and then temperature in use is 200~230 DEG C of superheated steam to it Heat 20~30min；（4）After treating above-mentioned heating, it is separately added into 100~200mL fatty alcohol polyoxyethylene ether, 160~190g carbon thereto Sour hydrogen ammonium and 10~20g isobutyl triethoxy silanes stir evenly, and 300~400mL normal propyl alcohols are then added in thereto, in temperature It is 120~160 DEG C to spend, and frequency is under the ultrasonic wave of 25~30kHz, stirs 3~7h, use quality score is in whipping process 45% sodium hydroxide solution ensures that its pH is 6.5~7.5；（5）It treats to filter after above-mentioned stirring, filtrate is rinsed 2~4 times using deionized water, then with water according to solid Liquor ratio 1:5, under 1000~1200r/min of rotating speed, after stirring 10~15min, white carbon slurry is obtained, by the hard charcoal black wash of gained Material obtains modified white carbon black after centrifugal spray drying.
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| CN101708856A (en) * | 2009-12-14 | 2010-05-19 | 广东工业大学 | Method for producing 13X type zeolite molecular sieve, potassium carbonate, white carbon black and quartz sand by using granite powder |
| CN101746777B (en) * | 2009-12-18 | 2011-08-03 | 广东工业大学 | Method for producing 4A type zeolite molecular sieve and quartz sand by utilizing granite powder and alkaline aluminum dross |
| CN104386701A (en) * | 2013-08-19 | 2015-03-04 | 魏强 | Fluidized bed technology for processing and separating ultrafine silicon dioxide micropowder from stone processing sawn mud |
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Effective date of registration: 20180523 Address after: 317306 8 Fuxin Road, Yongan industrial agglomeration area, Fuying street, Xianju, Taizhou, Zhejiang Applicant after: Zhejiang Hongyun rubber and Plastic Co., Ltd. Address before: 213164 room 1202, unit 5, Xinli Park, Xinbei District, Changzhou, Jiangsu Applicant before: Gao Dayuan |
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