CN103466640A - Method for reducing specific surface area BET (Brunauer Emmet Teller) of white carbon black prepared by using sulfuric acid precipitation method - Google Patents
Method for reducing specific surface area BET (Brunauer Emmet Teller) of white carbon black prepared by using sulfuric acid precipitation method Download PDFInfo
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Abstract
The invention discloses a method for reducing the specific surface area BET (Brunauer Emmet Teller) of white carbon black prepared by using a sulfuric acid precipitation method. The method comprises the following steps of improving the mass concentration of sodium silicate for reaction, and/or increasing pH value during aging. Specifically, the specific surface area BET of the white carbon black prepared by adopting the sulfuric acid precipitation method can be reduced by improving the mass concentration of the sodium silicate to 20-35 percent and increasing the pH value during aging to 4-10. According to the method, not only can the specific surface area BET of the white carbon black be remarkably reduced, but also accurate control over the specific surface area BET of the white carbon black can be realized, and the requirements on the white carbon black with lower specific surface area in related fields are met. The method disclosed by the invention is simple to operate, easy to implement and suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the white carbon black preparing technical field, be specifically related to a kind of method that reduces the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system.
Background technology
White carbon black is the general name of white powder X-ray amorphous silicic acid and silicate product, mainly refers to precipitated silica, aerosil, superfine silicon dioxide gel and aerogel, also comprises Powdered synthetic aluminium silicate and Calucium Silicate powder etc.White carbon black is porous material, and it forms available SiO
2nH
2o means, wherein nH
2o is that the form with surface hydroxyl exists.White carbon black can be dissolved in caustic alkali and hydrofluoric acid, the acid beyond water insoluble, solvent and hydrofluoric acid, have high temperature resistant, do not fire, tasteless, odorless, good electrical insulating property.White carbon black, as the auxiliary agent of a kind of environmental protection, excellent performance, is mainly used in rubber item (comprising high-temperature silicon disulfide rubber), weaving, papermaking, agricultural chemicals, foodstuff additive field.
White carbon black is divided into precipitated silica and thermal silica substantially by production method.For the gluey nanoparticle (particle diameter is less than 100nm) of the amorphous cotton-shaped translucent solid of white, nontoxic under the thermal silica normality, huge specific surface area is arranged.Thermal silica is all nano silicon, and product purity can reach 99%, and particle diameter can reach 10～20nm, but complicated process of preparation is expensive.Precipitated silica is divided into again traditional precipitated silica and special precipitation white carbon black, and the former refers to sulfuric acid, hydrochloric acid, CO
2with the silicon-dioxide that water glass is basic raw material production, the latter refers to the silicon-dioxide that special methods such as adopting high-gravity technology, sol-gel method, chemical crystal method, secondary crystal method or reversed phase micelle microemulsion method are produced.Precipitated silica is mainly as natural rubber and elastomeric strengthening agent, toothpaste abrasives etc.Thermal silica is mainly as strengthening agent, coating and the unsaturated polyester thickening material of silicon rubber, and superfine silicon dioxide gel and aerogel are mainly as Coating Matting agent, thickening material, plastic film open agent etc.
(1) vapor phase process
Be mainly chemical vapour deposition (CAV) method, claim again pyrolysis method, dry method or combustion method.Its raw material is generally silicon tetrachloride, oxygen (or air) and hydrogen, and under high temperature, reaction forms.Reaction formula is:
SiCl
4+2H
2+O
2→SiO
2+4HCl。
(2) precipitator method
The precipitator method are again the water glass acidization, adopt water glass solution and acid-respons, through precipitation, filtration, washing, drying and calcining, obtain white carbon black.Reaction formula is:
Na
2siO
3+ 2H
+→ white carbon black+2Na
++ H
2o.
The common precipitator method are sulfuric acid precipitation methods, even react with sulphuric acid soln with water glass solution, generate white carbon black.For example Chinese patent CN102092721A discloses a kind of method of preparing nanoscale white carbon black through sulfuric acid precipitation method, take water glass as raw material, utilize sulfuric acid for precipitation agent, the hydrolysis rate by tensio-active agent and dispersion aids regulation and control silicate and the polymerization degree of silicic acid molecule prepare high-quality nano-scale white carbon black.Chinese patent CN102897773A discloses a kind of preparation method and white carbon black of white carbon black, is also to utilize sulfuric acid for precipitation agent, utilizes water glass for the raw material production white carbon black.Chinese patent CN102951649A discloses a kind of preparation method of modified white carbon black, utilizes water glass to generate white carbon black with reacting of sulfuric acid.
At present, although there is the method for the standby white carbon black of many sulfuric acid precipitation legal systems open, but each important parameter research not in the dialogue manufacturing technologies of carbon black, with clear and definite its to product performance, especially the impact of the key property such as specific surface area BET and oil-absorption(number) DBP, these performances directly determine the effect of white carbon black product in different field, therefore furtheing investigate the sulfuric acid precipitation legal system significant on the impact of product performance for each important parameter in the production technique of white carbon black, is also the problem that this area is needed solution badly.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of method that reduces the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system, the method is by realizing the reduction of white carbon black specific surface area BET with the regulation and control of the pH value of the mass concentration of water glass and/or ageing to reaction.
For realizing purpose of the present invention, the present invention by the following technical solutions:
A kind of method that reduces the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system comprises: improve the mass concentration of reaction with water glass; And/or the pH value of raising ageing.
The further investigation of the applicant's process finds no matter be to improve reaction all can reduce the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system by the mass concentration of water glass or the pH value of raising ageing, therefore the present invention can adopt in these two kinds of means any, or by two kinds of means combinations.
In method provided by the invention, the mass concentration of described water glass is brought up to 20%～35%, for example 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, preferably 22%～32%, more preferably 25%～30%, most preferably 25%～28%.
In method provided by the invention, the pH value of described ageing is brought up to 4～10, for example 4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9,9.5,10, preferably 5～9, more preferably 6～8, most preferably 6～7.
Method provided by the invention can comprise the following steps:
(1) water glass solution that the preparation mass concentration is 20%～35%;
(2) described water glass solution and sulphuric acid soln are mixed in reactor, under pH8～11,80～98 ℃ of conditions of temperature, react 60～150min;
(3) pH of reaction solution is adjusted to 4～10, under 80～98 ℃ of conditions of temperature, ageing 30～120min, obtain slip;
(4) pH of described slurry is adjusted to 2～5, through press filtration, pulp and drying, obtains the white carbon black finished product.
Preferably, the modulus of water glass is 3.0～4.0 in described step (1), for example 3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9,4.0, preferably 3.2～3.8, more preferably 3.2～3.5.
Preferably, described step (1) is specially:
(1a) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(1b) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 20～35%, standby.
Preferably, the concentration of sulphuric acid soln is 40%～98% in described step (2), for example 40%, 42%, 48%, 50%, 55%, 60%, 70%, 75%, 78%, 80%, 85%, 90%, 95%, 98%, preferably 98%.
Preferably, pH is 9～11 in described step (2), for example 9.2,9.5,9.8,10,10.2,10.5,10.8,11, preferably 10～11, more preferably 10.
Preferably, in described step (2), temperature is 85～96 ℃, for example 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, and preferably 88～95 ℃, more preferably 94 ℃.
Preferably, in described step (2), the time of reaction is 80～120min, for example 80min, 85min, 90min, 95min, 100min, 105min, 110min, 115min, 120min, preferably 90～110min, more preferably 95～105min.
Preferably, in described step (3), the temperature of ageing is 85～96 ℃, for example 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, and preferably 88～95 ℃, more preferably 94 ℃.
Preferably, in described step (3), the time of ageing is 45～100min, for example 45min, 50min, 60min, 70min, 75min, 80min, 85min, 90min, 95min, 100min, preferably 60～90min, more preferably 70～80min.
Preferably, the pH in described step (4) is 2.2,2.5,2.8,3.2,3.5,3.8,4.2,4.5,4.8,4.9.
Preferably, press filtration is specially in described step (4): carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake.
Preferably, in described step (4), pulp is specially: in the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator.
Preferably, drying is specially in described step (4): in drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product.
Preferably, described step (1) also comprises: add sodium-chlor in described water glass solution, fully dissolve.
Further preferably, the content of described sodium-chlor is 0～300g/L, for example 10g/L, 20g/L, 50g/L, 80g/L, 100g/L, 120g/L, 150g/L, 180g/L, 210g/L, 230g/L, 250g/L, 280g/L, 290g/L, 300g/L, preferred 10～250g/L, more preferably 50～200g/L, most preferably 100～150g/L.
Add ionogen sodium-chlor and nonproductive in necessary key element, whether reality is selected to add as required, and ionogen is not limited to sodium-chlor, can also be Repone K, sodium sulfate etc.
In an optimal technical scheme of the present invention, described method comprises:
(a) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(b) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 20～35%;
(c) described water glass solution and sulphuric acid soln are mixed in reactor, under pH8～11,80～98 ℃ of conditions of temperature, react 60～150min;
(d) pH of reaction solution is adjusted to 4～10, under 80～98 ℃ of conditions of temperature, ageing 30～120min, obtain slip;
(e) pH of described slurry is adjusted to 2～5; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product.
In another optimal technical scheme of the present invention, described method comprises:
(a ') adds solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(b ') adds water by the described liquid soluble glass dissolved, is diluted to the water glass solution that mass concentration is 20～35% in the water glass adjustment tank, add sodium-chlor simultaneously and fully dissolve, to the content of sodium-chlor be 0～300g/L;
(c ') described water glass solution and sulphuric acid soln are mixed in reactor, under pH8～11,80～98 ℃ of conditions of temperature, react 60～150min;
(d ') pH of reaction solution is adjusted to 4～10, under 80～98 ℃ of conditions of temperature, ageing 30～120min, obtain slip;
(e ') pH of described slurry is adjusted to 2～5; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product.
" water glass " that this paper mentions and " water glass " reality are the different names of same substance, and can refer to simple for example solid kind material (containing hydrate) according to concrete use scenes, also can refer to the aqueous solution.
Useful technique effect of the present invention:
The applicant finds through further investigation: improve reaction and can reduce the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system by the mass concentration of water glass and/or the pH value that improves ageing, clearly illustrated the impact of sulfuric acid precipitation legal system for these two factor dialogue carbon black specific surface BET of pH value of the mass concentration of water glass in white carbon black technique and ageing.Apply method of the present invention, can significantly reduce white carbon black specific surface area BET, and realize the accurate control of white carbon black specific surface area BET, meet the demand of association area to the white carbon black of low specific surface area.Method of the present invention is simple to operate, is easy to realize, is applicable to large-scale industrial production.
The accompanying drawing explanation
The technical route figure that Fig. 1 is the standby white carbon black of sulfuric acid precipitation legal system.
Fig. 2 is the data plot of sodium silicate silicate with respect to specific surface area BET and oil-absorption(number) DBP.
Fig. 3 is the data plot of reaction pH with respect to specific surface area BET and oil-absorption(number) DBP.
Fig. 4 is the data plot of temperature of reaction with respect to specific surface area BET and oil-absorption(number) DBP.
Fig. 5 is that the NaCl relative concentration is in the data plot of specific surface area BET and oil-absorption(number) DBP.
Fig. 6 is the data plot of ageing pH with respect to specific surface area BET and oil-absorption(number) DBP.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail.It will be understood to those of skill in the art that the following examples are only for the present invention is described, and should not be considered as limiting scope of the present invention.Unreceipted concrete technology or condition person in embodiment, according to the described technology of the document in this area or condition, or carry out according to product description.The unreceipted person of production firm of agents useful for same or instrument, being can be by the conventional products of commercial acquisition.The present invention adopts the technical route shown in Fig. 1 to prepare white carbon black.
The impact of embodiment 1 research processing parameter on specific surface area BET and the oil-absorption(number) DBP of white carbon black
This experiment adopts L
16(4
5) quadrature studied water glass (water glass) concentration, reaction pH, temperature of reaction, sodium chloride concentration and five factors of ageing pH to the impact of specific surface area BET and the oil-absorption(number) DBP of white carbon black, by data analysis, draws detailed conclusion.
Concrete experimentation is substantially as follows:
(1) sodium silicate solution of configuration 200mL finite concentration (table 1 mesosilicic acid na concn), pour in the 500mL there-necked flask, adds a certain amount of (NaCl concentration in table 1) NaCl solid; Diluting concentrated sulfuric acid is become to 40% concentration.
(2) liquid at the bottom of reaction solution is warming up to certain temperature (temperature of reaction in table 1), drips while stirring sulfuric acid, conditioned reaction liquid pH, until complete white flocks occurs, control and record in reaction end pH(table 1 and react pH); Again regulate material liquid pH to acid (ageing pH in table 1), ageing 60min under said temperature.
(3) feed liquid is carried out to suction filtration, gained wet cake water repetitive scrubbing is to till can't check Cl-, and wet cake is directly dried, and then pulverizes and obtains white carbon black product.
(4) adopt the method measurement the specific area BET in HG/T3073-2008, adopt the method in HG/T3072-2008 to measure oil-absorption(number) DBP.
Table 1 orthogonal experiment factor and level
Annotate:
awater glass (Na
2siO
39H
2o, 0.14～0.35M).
Orthogonal and result are as shown in table 2, carry out altogether the experiment of 16 groups of (numbering 1～16) different factors combine, every group of parallel laboratory test three times, and specific surface area BET and the oil-absorption(number) DBP of the white carbon black that test makes, get the mean value of three times, is summarized as follows table 2.
Table 2 orthogonal and result
Annotate:
b1 means factor A(sodium silicate silicate herein) level (corresponding to table 1) be 1(40g/L), all the other are by that analogy.
The result that result shown in table 2 (BET and DBP) is obtained when each specified level according to each specific factor is averaged, and is summarized in table 3.
Table 3 orthogonal experiment data processing
Annotate:
cbET herein
1mean that certain factor is when level 1, the mean value of the experimental result specific surface area BET obtained, for example 80.25 of the upper left corner mean factor A(sodium silicate silicates) be horizontal 1(40g/L) time, the mean value of four groups of experiments (numbering 1～4 in table 2) specific surface area BET, all the other are by that analogy.
dbET herein
extreme differencemean that certain factor is respectively when 4 different levelss, the extreme difference of the experimental result specific surface area BET obtained, i.e. extreme difference between level, all the other are by that analogy.
ethe situation of the mean value maximum of the specific surface area BET that optimum certain factor of expression obtains when certain level herein, such as A2 means factor A(sodium silicate silicate) in horizontal 2(60g/L) time, the mean value maximum of the specific surface area BET obtained, all the other by that analogy.
According to the data shown in table 3, map respectively: factor A(sodium silicate silicate) with respect to the data plot (as Fig. 2) of specific surface area BET and oil-absorption(number) DBP; Factor B(reacts pH) with respect to the data plot (as Fig. 3) of specific surface area BET and oil-absorption(number) DBP; Factor C(temperature of reaction) with respect to the data plot (as Fig. 4) of specific surface area BET and oil-absorption(number) DBP; Factor D(NaCl concentration) with respect to the data plot (as Fig. 5) of specific surface area BET and oil-absorption(number) DBP; Factor E(ageing pH) with respect to the data plot (as Fig. 6) of specific surface area BET and oil-absorption(number) DBP.
As shown in Figure 2: sodium silicate silicate is when 60g/L is following, and BET increases with the increase of sodium silicate silicate, and sodium silicate silicate is when 60g/L is above, and BET reduces with the increase of sodium silicate silicate.In actual production, sodium silicate silicate generally all more than 60g/L, therefore can reduce the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system by the mode that improves sodium silicate silicate.
As shown in Figure 3: reaction pH is 7.0 when above, and BET reduces with the increase of reaction pH, and in actual production, pH is generally more than 7.0 in reaction, so the mode that can react pH by raising reduces the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system.
As shown in Figure 4: temperature of reaction is more than 70 ℃ the time, BET reduces with the increase of temperature of reaction, in actual production, temperature of reaction, generally all more than 70 ℃, therefore can reduce the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system by the mode that improves temperature of reaction.
As shown in Figure 5: NaCl concentration and BET are certain dependency, and NaCl concentration is when 80g/L is following, and BET has reducing to a certain degree with the increase of NaCl concentration; NaCl concentration is between 80g/L to 120g/L the time, and BET has increase to a certain degree with the increase of NaCl concentration; NaCl concentration is when 120g/L is above, and BET has reducing to a certain degree with the increase of NaCl concentration; Therefore can reduce the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system by the mode of appropriate interpolation NaCl.
As shown in Figure 6: ageing pH is 3.0 when above, and BET reduces with the increase of ageing pH, and in actual production, ageing pH, generally more than 3.0, therefore can reduce the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system by the mode that improves ageing pH.
Embodiment 2 BET are 117m
2the production of the white carbon black of/g
(1) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(2) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 22%;
(3) described water glass solution and sulphuric acid soln are mixed in reactor, under pH10,94 ℃ of conditions of temperature, reaction 60min;
(4) pH of reaction solution is adjusted to 6, under 94 ℃ of conditions of temperature, ageing 60min, obtain slip;
(5) pH of described slurry is adjusted to 3; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product;
(6) adopting the method measurement the specific area BET in HG/T3073-2008 is 117m
2/ g.
Embodiment 3 BET are 110m
2the production of the white carbon black of/g
(1) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(2) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 20%;
(3) described water glass solution and sulphuric acid soln are mixed in reactor, under pH10,94 ℃ of conditions of temperature, reaction 60min;
(4) pH of reaction solution is adjusted to 7, under 94 ℃ of conditions of temperature, ageing 60min, obtain slip;
(5) pH of described slurry is adjusted to 3; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product;
(6) adopting the method measurement the specific area BET in HG/T3073-2008 is 110m
2/ g.
Embodiment 4 BET are 100m
2the production of the white carbon black of/g
(1) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(2) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 30%;
(3) described water glass solution and sulphuric acid soln are mixed in reactor, under pH10,94 ℃ of conditions of temperature, reaction 60min;
(4) pH of reaction solution is adjusted to 7, under 94 ℃ of conditions of temperature, ageing 60min, obtain slip;
(5) pH of described slurry is adjusted to 3; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product;
(6) adopting the method measurement the specific area BET in HG/T3073-2008 is 100m
2/ g.
Embodiment 5 BET are 94m
2the production of the white carbon black of/g
(1) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(2) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 35%;
(3) described water glass solution and sulphuric acid soln are mixed in reactor, under pH10,94 ℃ of conditions of temperature, reaction 60min;
(4) pH of reaction solution is adjusted to 10, under 94 ℃ of conditions of temperature, ageing 60min, obtain slip;
(5) pH of described slurry is adjusted to 3; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product;
(6) adopting the method measurement the specific area BET in HG/T3073-2008 is 94m
2/ g.
Embodiment 6 BET are 180m
2the production of the white carbon black of/g
(1) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(2) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 25%;
(3) described water glass solution and sulphuric acid soln are mixed in reactor, under pH8,84 ℃ of conditions of temperature, reaction 150min;
(4) pH of reaction solution is adjusted to 4, under 84 ℃ of conditions of temperature, ageing 60min, obtain slip;
(5) pH of described slurry is adjusted to 2; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product;
(6) adopting the method measurement the specific area BET in HG/T3073-2008 is 180m
2/ g.
Embodiment 7 BET are 165m
2the production of the white carbon black of/g
(1) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(2) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 20%;
(3) described water glass solution and sulphuric acid soln are mixed in reactor, under pH8,84 ℃ of conditions of temperature, reaction 150min;
(4) pH of reaction solution is adjusted to 5, under 84 ℃ of conditions of temperature, ageing 60min, obtain slip;
(5) pH of described slurry is adjusted to 2; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product;
(6) adopting the method measurement the specific area BET in HG/T3073-2008 is 165m
2/ g.
Embodiment 8 BET are 150m
2the production of the white carbon black of/g
(1) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(2) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 35%;
(3) described water glass solution and sulphuric acid soln are mixed in reactor, under pH8,84 ℃ of conditions of temperature, reaction 150min;
(4) pH of reaction solution is adjusted to 5, under 84 ℃ of conditions of temperature, ageing 60min, obtain slip;
(5) pH of described slurry is adjusted to 2; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product;
(6) adopting the method measurement the specific area BET in HG/T3073-2008 is 150m
2/ g.
Embodiment 9 BET are 142m
2the production of the white carbon black of/g
(1) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(2) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 30%;
(3) described water glass solution and sulphuric acid soln are mixed in reactor, under pH10,84 ℃ of conditions of temperature, reaction 150min;
(4) pH of reaction solution is adjusted to 5, under 84 ℃ of conditions of temperature, ageing 60min, obtain slip;
(5) pH of described slurry is adjusted to 2; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product;
(6) adopting the method measurement the specific area BET in HG/T3073-2008 is 142m
2/ g.
Comparative Examples 1 BET is 120m
2the production of the white carbon black of/g
(1) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(2) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 20%;
(3) described water glass solution and sulphuric acid soln are mixed in reactor, under pH10,94 ℃ of conditions of temperature, reaction 60min;
(4) pH of reaction solution is adjusted to 6, under 94 ℃ of conditions of temperature, ageing 60min, obtain slip;
(5) pH of described slurry is adjusted to 3; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product;
(6) adopting the method measurement the specific area BET in HG/T3073-2008 is 120m
2/ g.
Comparative Examples 2 BET are 200m
2the production of the white carbon black of/g
(1) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(2) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 20%;
(3) described water glass solution and sulphuric acid soln are mixed in reactor, under pH8,84 ℃ of conditions of temperature, reaction 150min;
(4) pH of reaction solution is adjusted to 4, under 84 ℃ of conditions of temperature, ageing 60min, obtain slip;
(5) pH of described slurry is adjusted to 2; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product;
(6) adopting the method measurement the specific area BET in HG/T3073-2008 is 200m
2/ g.
By embodiment 2～5, with Comparative Examples 1, compare, embodiment 6～9 relatively can find out with Comparative Examples 2: improve and react by the mass concentration of water glass or the pH value of raising ageing, all can reduce the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system.
Applicant's statement, the present invention illustrates detailed method of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed method, does not mean that the present invention must rely on above-mentioned detailed method and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a method that reduces the standby white carbon black specific surface area BET of sulfuric acid precipitation legal system, is characterized in that, described method comprises: improve the mass concentration of reaction with water glass; And/or the pH value of raising ageing.
2. method according to claim 1, is characterized in that, the mass concentration of described water glass is brought up to 20%～35%, preferably 22%～32%, more preferably 25%～30%, most preferably 25%～28%;
Preferably, the pH value of described ageing is brought up to 4～10, preferably 5～9, more preferably 6～8, most preferably 6～7.
3. method according to claim 1 and 2, is characterized in that, said method comprising the steps of:
(1) water glass solution that the preparation mass concentration is 20%～35%;
(2) described water glass solution and sulphuric acid soln are mixed in reactor, under pH8～11,80～98 ℃ of conditions of temperature, react 60～150min;
(3) pH of reaction solution is adjusted to 4～10, under 80～98 ℃ of conditions of temperature, ageing 30～120min, obtain slip;
(4) pH of described slurry is adjusted to 2～5, through press filtration, pulp and drying, obtains the white carbon black finished product.
4. method according to claim 3, is characterized in that, in described step (1), the modulus of water glass is 3.0～4.0, preferably 3.2～3.8, more preferably 3.2～3.5;
Preferably, described step (1) is specially:
(1a) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(1b) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 20～35%, standby.
5. according to the described method of claim 3 or 4, it is characterized in that, in described step (2), the concentration of sulphuric acid soln is 40%～98%, preferably 98%;
Preferably, in described step (2), pH is 9～11, preferably 10～11, more preferably 10;
Preferably, in described step (2), temperature is 85～96 ℃, preferably 88～95 ℃, more preferably 94 ℃;
Preferably, the time of reaction is 80～120min, preferably 90～110min, more preferably 95～105min in described step (2).
6. according to the described method of any one in claim 3 to 5, it is characterized in that, in described step (3), the temperature of ageing is 85～96 ℃, preferably 88～95 ℃, more preferably 94 ℃;
Preferably, the time of ageing is 45～100min, preferably 60～90min, more preferably 70～80min in described step (3).
7. according to the described method of any one in claim 3 to 6, it is characterized in that, press filtration is specially in described step (4): carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake;
Preferably, in described step (4), pulp is specially: in the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator;
Preferably, drying is specially in described step (4): in drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product.
8. according to the described method of any one in claim 3 to 7, it is characterized in that, described step (1) also comprises: add sodium-chlor in described water glass solution, fully dissolve;
Preferably, the content of described sodium-chlor is 0～300g/L, preferably 10～250g/L, more preferably 50～200g/L, 100～150g/L most preferably.
9. according to the described method of any one in claim 3 to 7, it is characterized in that, described method comprises:
(a) add solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(b) the described liquid soluble glass dissolved is added to water in the water glass adjustment tank, be diluted to the water glass solution that mass concentration is 20～35%;
(c) described water glass solution and sulphuric acid soln are mixed in reactor, under pH8～11,80～98 ℃ of conditions of temperature, react 60～150min;
(d) pH of reaction solution is adjusted to 4～10, under 80～98 ℃ of conditions of temperature, ageing 30～120min, obtain slip;
(e) pH of described slurry is adjusted to 2～5; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product.
10. according to the described method of any one in claim 3 to 9, it is characterized in that, described method comprises:
(a ') adds solid water glass and water in dissolution kettle, pass into steam that pressure is greater than 0.7Mpa in dissolution kettle to the dissolution kettle internal pressure be steam off after 0.5～0.6Mpa, be incubated 2～3 hours, being dissolved into mass concentration is the liquid soluble glass more than 35%;
(b ') adds water by the described liquid soluble glass dissolved, is diluted to the water glass solution that mass concentration is 20～35% in the water glass adjustment tank, add sodium-chlor simultaneously and fully dissolve, to the content of sodium-chlor be 0～300g/L;
(c ') described water glass solution and sulphuric acid soln are mixed in reactor, under pH8～11,80～98 ℃ of conditions of temperature, react 60～150min;
(d ') pH of reaction solution is adjusted to 4～10, under 80～98 ℃ of conditions of temperature, ageing 30～120min, obtain slip;
(e ') pH of described slurry is adjusted to 2～5; Carry out press filtration by pressure filter, then washing, with filtering part water and wash away sodium sulfate impurity, make filter cake; In the pulp tank, the filter cake made is stirred and becomes flowable slip by agitator; In drying tower, by warm air, the slip of atomization is carried out to drying and remove moisture, make the white carbon black finished product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107055557A (en) * | 2017-05-04 | 2017-08-18 | 无锡恒诚硅业有限公司 | A kind of preparation method of the white carbon of controllable CTAB specific surface areas |
| CN108190900A (en) * | 2018-03-29 | 2018-06-22 | 广州市飞雪材料科技有限公司 | A kind of low specific surface area high oil absorption value friction type silica and preparation method thereof |
| CN111017932A (en) * | 2019-12-30 | 2020-04-17 | 无锡恒诚硅业有限公司 | Large-aperture white carbon black and preparation method and application thereof |
| CN111484025A (en) * | 2020-04-14 | 2020-08-04 | 广州市飞雪材料科技有限公司 | Preparation method of silicon dioxide for low-specific-surface-area high-density thickening toothpaste |
| CN112573524A (en) * | 2020-12-29 | 2021-03-30 | 无锡恒诚硅业有限公司 | Precipitated silica, and preparation method and application thereof |
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| CN101786633A (en) * | 2010-02-26 | 2010-07-28 | 无锡恒诚硅业有限公司 | Production technology of white microbead-shaped white carbon black |
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| CN101774591A (en) * | 2010-02-26 | 2010-07-14 | 无锡恒诚硅业有限公司 | Production technology of white microsphere high-strength white carbon black |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107055557A (en) * | 2017-05-04 | 2017-08-18 | 无锡恒诚硅业有限公司 | A kind of preparation method of the white carbon of controllable CTAB specific surface areas |
| CN108190900A (en) * | 2018-03-29 | 2018-06-22 | 广州市飞雪材料科技有限公司 | A kind of low specific surface area high oil absorption value friction type silica and preparation method thereof |
| CN111017932A (en) * | 2019-12-30 | 2020-04-17 | 无锡恒诚硅业有限公司 | Large-aperture white carbon black and preparation method and application thereof |
| CN111017932B (en) * | 2019-12-30 | 2023-02-21 | 无锡恒诚硅业有限公司 | Large-aperture white carbon black and preparation method and application thereof |
| CN111484025A (en) * | 2020-04-14 | 2020-08-04 | 广州市飞雪材料科技有限公司 | Preparation method of silicon dioxide for low-specific-surface-area high-density thickening toothpaste |
| CN111484025B (en) * | 2020-04-14 | 2020-11-17 | 广州市飞雪材料科技有限公司 | Preparation method of silicon dioxide for low-specific-surface-area high-density thickening toothpaste |
| CN112573524A (en) * | 2020-12-29 | 2021-03-30 | 无锡恒诚硅业有限公司 | Precipitated silica, and preparation method and application thereof |
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