CN102137813A - Process for preparing precipitated silicas, precipitated silicas and their use - Google Patents
Process for preparing precipitated silicas, precipitated silicas and their use Download PDFInfo
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- CN102137813A CN102137813A CN2008801309227A CN200880130922A CN102137813A CN 102137813 A CN102137813 A CN 102137813A CN 2008801309227 A CN2008801309227 A CN 2008801309227A CN 200880130922 A CN200880130922 A CN 200880130922A CN 102137813 A CN102137813 A CN 102137813A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
- C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
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Abstract
The present invention relates to a process for preparing precipitated silicas, precipitated silicas and their use as a filler in an elastomer. The process comprises the steps of: preparing initial charge; simultaneously metering silicate and acidifying agent into the initial charge and reacidifying the precipitation suspension to a pH of 2.5 to 6.0, wherein the silicate used has metal oxide of 4wt%-7wt% and silicon dioxide of 14wt%-23wt% and the acidifying agent is selected from the group consisting of sulphuric acid of 90wt%-98.5wt%, hydrochloric acid of 34wt%-42.7wt%, nitric acid of 60wt%-68wt%, phosphoric acid of 80wt%-100wt%, carbonic acid or CO2 and sodium hydrogen sulphite or SO2.
Description
The present invention relates to prepare precipitated silica novel method, relate to precipitated silica of novelty and uses thereof.
Precipitated silica is to regulate the speciality chemical of its character according to required Application Areas.This species diversity and mutability make precipitated silica nowadays be used for many Application Areass.At Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH ﹠amp; Co. KGaA, Online Edition, DOI (Digital Object Identifier): 10.1002/14356007.a23_583.pub3,2008, specified the example in the chapters and sections 7.4.
The character of precipitated silica is by their preparation method's decision.The preparation method can roughly be subdivided into settling step and post precipitation treatment step again.
A series of known intermediate processings are arranged.In a kind of variant, for example, mineral acid is added in the initial charge of alkali metal silicate solutions.Can as sodium-chlor or sodium sulfate, add to and change this method in the alkali metal silicate solutions for example by with strong acid and alkaline neutral salt.
At present main other method that adopts is characterised in that, by with two kinds of reactive components, promptly silicate solutions and souring agent add to simultaneously and implement precipitation in the initial charge.This initial charge can be made of water, but also can be made of the part of described silicate solutions and/or electrolyte solution.These preparation methods (wherein adding reactive component simultaneously) usually carry out under constant pH or under constant base number.Precipitation under constant base number is meant that the concentration of the sodium ion that can freely obtain in the reaction soln keeps constant.For example, owing to, discharge sodium ion with the sodium sulfate form, but sodium ion is incorporated also in the silicate agglomerate of formation into for example reaction of the acid-alkali in the water glass process of sulfuric acid precipitation.Because these two kinds are reflected at the kinetics aspect and move independently of one another, so the precipitation process under constant pH is different from the precipitation of base number control.It also is known that PH and base number do not keep the constant method.
Another variant of precipitin reaction relates to the use growth cores.In this case, at first, in " preliminary precipitation reaction ", in initial charge, form little silicon dioxide granule, implement precipitation by adding acid and silicate simultaneously subsequently.In this case, also can keep the constant precipitation of controlling itself by making pH or base number.The example sees EP 0520862 B1, EP 0670813 B1, EP 0670814 B1 or EP 0917519 B1.These methods are very consuming time, because " preliminary precipitation " constitutes additional process steps.
Other precipitation control possibility is aging step and/or the variation of reactant feed rate in precipitation process.Therefore, for example, EP 1 764 344 A1 have described the method that forms different primary particles owing to different settling rates, and the result when precipitation finishes, obtains silica suspension, and wherein silicon-dioxide has the character of two kinds of different precipitated silicas concurrently.
The aforesaid method variant is only represented the selection in the multiple known precipitator method.Except that the variant of the precipitator method, equal a large amount of post treatment method variant is arranged, making whole preparation method thus is that the almost method of infinite variant is arranged.These methods in most of the cases produce the product of high specialization, can only be used for clear and definite limited Application Areas in each case but shortcoming is these products specialization like this so that they.This means that again the productivity of each product reduces, and therefore, must frequently switch all the time and produce, and this is again consuming time and expensive.
Another shortcoming for preparing many currently known methodss of the precipitated silica with special properties is the complicacy of intermediate processing.For example, in some cases, must carry out two or more precipitations side by side,, influence the complicacy and the cost of this equipment thus unfriendly after this with suspension combination again.Stop the adding of step and the use of different settling rates and the Space-Time yield is had negative impact and/or make the effort that relates in the control complicated, improve easily error property thus.
Therefore, an object of the present invention is to provide the simple method of preparation precipitated silica, but it still can prepare the precipitated silica that shows outstanding application performance in wide range of application.For example, in specific purposes of the present invention, intention is should have not only as the tire filler also as the good character of the filler in mechanical rubber item such as the sole by the precipitated silica that this novel method obtains.From the whole contents of following description, embodiment and claim, can find out other purpose of clearly not stating.
It is evident that, to being different from requirement as the requirement of the precipitated silica of the filler in the doughnut to the precipitated silica that mixes sole.For example, the precipitated silica in the doughnut should be guaranteed effective reinforcement veritably, also should guarantee low-rolling-resistance, allows to reduce the fuel consumption of vehicle thus.And in sole, precipitated silica must mainly show reinforcement character, also must guarantee the wearing quality (wear-resisting) of sole.These character are similar to the requirement to tire veritably, but because the difference of rubber compound is formed, all do not produce same good effect in these two systems.
After a large amount of research work, have been found that now surprisingly, by careful selection reactant and prudent control precipitin reaction, can obtain to realize the precipitated silica of above-mentioned purpose.
The present invention correspondingly provides the method for preparing precipitated silica, and it comprises the following steps:
A) initial charge of the aqueous solution of preparation water or alkalimetal silicate and/or alkaline earth metal silicate,
B) at 80 to 100 ℃, alkalimetal silicate and/or alkaline earth metal silicate and souring agent metering are simultaneously under agitation added in this initial charge,
C) will precipitate suspension and be acidified to 2.5 to 6.0 pH again,
D) filter, wash and drying,
And it is characterized in that step a) and/or b) in used alkalimetal silicate and/or alkaline earth metal silicate alkalimetal oxide and/or the dioxide-containing silica of alkaline earth metal oxide content and 14 weight % to 23 weight % with 4 weight % to 7 weight %, be characterised in that step b) and/or c) in used souring agent be that to be selected from by concentration be the sulfuric acid of 90 weight % to 98.5 weight %, concentration is the hydrochloric acid of 34 weight % to 42.7 weight %, concentration is the nitric acid of 60 weight % to 68 weight %, concentration is the phosphoric acid of 80 weight % to 100 weight % and carbonic acid (or the CO that is in corresponding possible concentration
2Gas) and sodium bisulfite (or SO
2Gas) souring agent of the group of Zu Chenging, and be characterised in that the pH(based on when beginning precipitation records at 60 ℃), the pH(of precipitation suspension records at 60 ℃) in precipitation process, reduce by 1% to 20%.
Optional can be at step c) and d) between gained suspension was stirred (afterstirred) 1 to 90 minute after 60 to 100 ℃.Step b) also can be chosen wantonly and interrupt 1 to 60 minute so that the gained silicon dioxide granule is aging, but typically this is not necessarily.
The present invention also provides can be by the precipitated silica of method acquisition of the present invention.
Last theme of the present invention is the purposes of precipitated silica of the present invention as the filler in the following goods: pneumatic tyre, and summer is with using tire and annual tyre surface with tire, tyres for passenger cars in tire, winter, the MPV tire, motorcycle tyre, carcass parts, cable sheath, flexible pipe, rotating band, travelling belt, roll cladding thing, sole, packing ring and damping element, and, more general ground, MRG(machinery rubber item).
Describe theme of the present invention below in detail.Term " silicate solutions " and " alkalimetal silicate and/or alkaline earth metal silicate solution " synonym use.
For example, with (wherein not only use dense silicate solutions such as the currently known methods among EP 1764344 A1, also use dense souring agent) difference, method of the present invention use with EP 1764344 A1 in used compare rare at least 10%, preferably at least 15%, more preferably at least 20% the more silicate solutions of dilution.The alkalimetal oxide of silicate solutions used according to the invention and/or alkaline earth metal oxide content are 4 weight % to 7 weight %, preferred 5 weight % to 6.5 weight %, more preferably 5.5 weight % to 6.5 weight %.Especially sodium silicate solution (water glass) and/or potassium silicate solution of used silicate solutions in the method for the present invention.
The dioxide-containing silica of silicate solutions used according to the invention is 14 weight % to 23 weight %, preferred 18 weight % to 22 weight %, more preferably 20 weight % to 22 weight % are therefore equally than in the ordinary method low at least 10%, preferably at least 15%, more preferably at least 20%.Modulus in the silicate solutions used according to the invention, promptly the weight ratio of silicon-dioxide and alkalimetal oxide and/or alkaline earth metal oxide is preferably 2.0 to 5.75, and more preferably 2.5 to 4.5, very preferably 3 to 4, preferred more especially 3.2 to 3.7.
Here, can note the following fact, promptly document has also comprised the description to the method for using rare water glass, for example EP 0520862 B1 and EP 0670813 B1.But, in these methods, two kinds of reactants, promptly silicate solutions and souring agent all use with the dilute solution form.The shortcoming of this method is that because general higher dilution factor, they show lower Space-Time yield and higher energy expenditure---on comparative sense, the water yield that must heat is much higher.In addition, based on this preparation mode, can only prepare be positioned at qualification/silicon-dioxide of narrow parameter area.
On the contrary, in the method for the invention, have only silicate solutions to use, and souring agent use with the strong solution form with the dilute solution form.Therefore can realize higher Space-Time yield and lower energy expenditure---on comparative sense, the water yield that must heat is lower.In addition, based on this preparation mode, can prepare the more silicon-dioxide of wide region.Be not limited by any one theory, but the inventor's viewpoint is,, occurs dissociation equilibrium at the utmost point in the short period of time usually when acid (one or more) when being rare.On the contrary, under the situation of sodium silicate solution, reach balance through a few hours.Therefore, also because the difference of water glass is formed, different products have been formed simultaneously.
As souring agent, preferred in the method for the invention dense mineral acid, example hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid or the CO of using
2Concentrated acid is meant 34 weight % to 42.7 weight %, the concentration of preferred 36 weight % to 40 weight % under the situation of hydrochloric acid; Under the vitriolic situation, be meant 90 weight % to 98.5 weight %, preferred 93 weight % to 98.5 weight %, the very preferably concentration of 96 weight % to 98 weight %; Under the situation of nitric acid, be meant the concentration of 60 weight % to 68 weight %; Under the situation of phosphoric acid, be meant 80 weight % to 100 weight %, preferred 80 weight % to 90 weight %, the more preferably concentration of 80 weight % to 85 weight %.
The inventor also has been found that, for method of the present invention basic be, during based on the precipitation beginning, pH when adding beginning when being silicate solutions and acid, the pH(of this precipitation suspension records at 60 ℃) must in precipitation process, reduce by 1% to 20%, preferred 2% to 15%, more preferably 3% to 10%, very preferably 5% to 10%." in precipitation process " is meant that the end that beginning of adding in silicate solutions and the acid is defined as starting point and adds with silicate solutions and acid the time is defined as terminal point.If will wear out in the method for the invention/maturation stage, then terminal point is meant the time point when adding for the last time silicate solutions and acid simultaneously in entire method.
Preferably 8 to 12, more preferably 9 to 11.5, very preferably regulate sedimentary beginning pH in 10 to 11 the scope.PH when precipitation finishes is preferably 6.5 to 11.5, and more preferably 7 to 11, very preferably 8 to 10.5, preferred especially 9 to 10, very particularly preferably 9.5 to 10.
Alkalimetal ion concentration in the reaction soln---with Y value representation---can keep constant or change in precipitation process in precipitation process.Chemical reaction in the Y value reflection precipitation process, more especially ion is incorporated silicon dioxide skeleton into.Can draw conclusion by this value, also can forecasting institute therefore even before the physico-chemical analysis of the finished product pay close attention to the quality and the reproducibility of product about the foundation structure of silicon-dioxide.Therefore, in a preferred variants of the present invention, precipitate so that the Y value in the precipitation process remains in 4 to 8 the scope.In first particularly preferred variant, the Y value in the precipitation process remains on 3 to 6, in preferred more especially 3.5 to 5.5 the scope.In second particularly preferred variant of method of the present invention, the Y value in the precipitation process keeps constant 6 to 8 in preferred especially 6 to 7.5 the scope.In a specific embodiments, advantageously verified, based on the Y value in when beginning precipitation, the Y value reduction in the precipitation process is maximum 25%, and more preferably 5% to 20%, preferred especially 10 to 15%.
Preferably precipitate 80 to 95 ℃ temperature.Pure sedimentation time, promptly add the time length of silicate solutions and souring agent simultaneously,---not considering break period---can be 50 to 80 minutes in a preferred variants of the present invention, is 80 to 120 minutes in another preferred variants of the present invention, more preferably 80 to 100 minutes.The feeding rate of selecting souring agent and silicate solutions is so that can keep required sedimentation time---and simultaneously, the required pH curve of precipitation suspension.
Can add at the same time before silicate solutions and the souring agent or among add ionogen.Being used for ionogen of the present invention is not incorporate amorphous SiO into
2Metal-salt in the skeleton or its aqueous solution, for example Na, K, Rb, Ba are vitriol, acetate, halogenide or carbonate form in each case.Electrolytical ratio is that 0.01 weight % –, 26 weight %(calculate with metal ion).
Also metal-salt or its solution can be added in the precipitation mixture, they incorporate SiO into
2In the skeleton, produce silicate thus.The ratio of these metal ions can be 0.5 weight % to 50 weight %, preferred 1 weight % to 10 weight %; Common ion is Al, Zr, Ti, Fe, Ca and Mg.
The precipitated silica suspension of making by method of the present invention filters in step d), and washes filter cake with water.
The filtration of silicon-dioxide of the present invention, liquefaction (for example according to DE 2447613) and the long-time or dry technician of being of short period of time are familiar with, and are found in the document of quoting in this specification sheets for example.Preferred so that the specific conductivity of the finished product＜2000 μ S/cm of the filtration of silicon-dioxide and washing, particularly＜1300 the mode of μ S/cm is carried out.
Silicon-dioxide of the present invention is preferably dry in pneumatic dryer, spray-dryer, stage drying device, belt dryer, B ü ttner moisture eliminator, swivel pipe moisture eliminator, flash distillation dryer, spin flash dryer or nozzle tower moisture eliminator.These dry variants comprise with spraying gun, single fluid or two-fluid spray nozzle or the operation of integrated fluid bed.Can for example carry out spraying drying according to US 4094771.Can for example described in EP 0937755, carry out nozzle tower drying.The content of US 4094771 and EP 0937755 is incorporated in the content of this specification sheets thus clearly.
Precipitated silica of the present invention can be to have 1 to 80 micron the granularity d that records by laser diffraction
50Powder type exist.Powder particle can have irregular or regular profile, and promptly they also can be substantially sphericals for example.Precipitated silica of the present invention is preferably has 80 microns to 1000 microns the granularity d that records by screenings analysis (Alpine)
50Substantially spherical particle (particulate) form.Under one situation of back, silicon-dioxide of the present invention preferably prepares by the nozzle tower desiccating method described in EP 0937755, and shows the distinctive profile of this desiccating method (seeing the accompanying drawing among the EP 0937755).The content of EP 0937755 is incorporated in the content of this specification sheets thus clearly.Precipitated silica of the present invention is preferably particle (d especially
501000 microns (Alpine screenings) forms), and the size-grade distribution that has after granulation makes: by screenings analysis (Ro-Tap), the particle of at least 80 weight % is greater than 300 microns, and no more than 10 weight % are less than 75 microns.
For example can use from Alexanderwerk AG, the roll squeezer of Remscheid carries out granulation.In this case, preferably under the situation of further not adding tackiness agent or liquid, this powder-product is outgased, and between the roller of two-sided installation, positioned vertical, evenly introduce via the horizontal feed system that contains list or twin screw by vacuum system.This is pressed into sheet product with powder, makes it reach required maximum particle size by grinding mill.
In a specific embodiments of the present invention, can grind precipitated silica of the present invention.The optional grinding technique of silicon-dioxide of the present invention is known to the skilled and for example is found in
Ullmann, the 5th edition, B2,5 – 20In order to grind silicon-dioxide of the present invention, the preferred use impacted grinding machine or opposed jet mill.The preferred abrasive parameters of selecting is so that the ground product has 1 to 15 micron, and preferred 3 to 10 microns, more preferably 4 to 10 microns the d that passes through that laser diffraction records based on the size distribution curve of volume
50Product of Yan Moing and unground product for example also can be used for the nonrubber purposes thus, for example are used for solid support material.
In another embodiment, the granularity of powder of the present invention is 15 to 80 microns.These powder especially preferably are applicable to the rubber product reinforcing purposes.
The precipitated silica that obtains by method of the present invention can be used as the filler in the following product: pneumatic tyre, summer is with using tire and annual tyre surface with tire, tyres for passenger cars, MPV tire in tire, winter, motorcycle tyre, the carcass parts, cable sheath, flexible pipe, rotating band, travelling belt, roll cladding thing, sole, packing ring and damping element.
The following example and process of measurement are intended to more sets forth in detail the present invention and do not limit its scope.
The mensuration of Y value:
Use sulfuric acid is as standardized solution and use phenolphthalein to measure the Y value as indicator.
Reagent
The concentration of-phenolphthalein in ethanol is the solution of 10 grams per liters
-concentration is the sulphuric acid soln of 1 mol
Program
With 100 milliliters of samples of being analyzed, for example precipitate suspension, place 500 milliliters of glass beakers, and add about 10 ml waters and 3-5 drips phenolphthalein solution.Use magnetic stirrer to stir this mixture, and use drop-burette adding sulphuric acid soln to become lightpink from redness until the phenolphthalein color.Adding 3-5 again drips phenolphthalein and continues titration.Repeat this process until not observing variable color again.
Following calculating Y value:
Y?=?V?×?N
Wherein:
The vitriolic volume that consumes in V=titration is in milliliter
The equivalent concentration of N=described acid
The mensuration of the pH of initial charge/precipitation suspension
Get initial charge of 50-100 milliliter or precipitation suspension sample and measure pH at 60 ℃ according to currently known methods.
The mensuration of filter cake solid content
This method is used for by removing the solid content that volatility is partly measured filter cake at 105 ℃.
Its relate to 100.00 the gram filter cakes (initial mass E) weigh up in the exsiccant teared porcelain boat (20 centimetres of diameters).If suitably, break filter cake into pieces to obtain to be not more than 1 cubic centimetre loose fragment with scraper.Sample is dried to constant weight at 105 ± 2 ℃ in loft drier.Subsequently, sample is cooled to room temperature with silica gel as siccative in the siccative case.Measure final quality A with gravimetry.
Solid content (SC) in % is determined as
SC?=?A/E?×100%，
A=wherein in the final quality of gram and E=in the initial mass of gram.
The mensuration of the solid content of silicon-dioxide charging
10 gram samples (initial mass E) are dried to constant weight at 120-140 ℃ under the infrared drying lamp in porcelain boat (45 millimeters of diameters).Subsequently sample is cooled to room temperature with silica gel as siccative in the siccative case.Measure final quality A with gravimetry.
Solid content (SC) in % is determined as
SC?=?A/E?×?100%，
A=wherein in the final quality of gram and E=in the initial mass of gram.
The mensuration of the pH of silicon-dioxide
In the revision of DIN EN ISO 787-9, measure the pH of silicon-dioxide with 5% form of suspension in water in room temperature.Relevant with the explanation of this standard, change initial mass (per 100 ml deionized water, 5.00 gram silicon-dioxide).
The mensuration of moisture content
In forcing air drying cabinet, measure the moisture content of silicon-dioxide after 2 hours 105 ℃ of dryings according to ISO 787-2.This drying loss mainly is made of moisture.
The mensuration of BET surface-area
(Str hlein JUWE) measures the ratio nitrogen surface area (below be called the BET surface-area) of Powdered, sphere-like or particulate silica to use the AREA-meter according to ISO 5794-1/Annex D.
The mensuration that ctab surface is long-pending
This method is based on according to ASTM 3765 or NFT 45-007(chapters and sections 5.12.1.3) method in, CTAB(N-hexadecyl-N, N, N-trimethylammonium bromide) be adsorbed on " outward " surface of silicon-dioxide.
In the aqueous solution, under stirring and supersound process, carry out the absorption of CTAB.Use the titration treater, by with NDSS(sulfo-succinic acid dioctyl sodium solution, " Aerosol OT " solution) back titration, measures the excessive not CTAB of absorption, terminal point shows with the maximum turbidity of solution and uses luminosity electrode (phototrode) mensuration.The temperature of all operations whole process of being carried out be 23-25 ℃ to prevent the CTAB crystallization.Back titration is based on following equation:
Device
METTLER Toledo DL 55 titration treaters and METTLER Toledo DL 70 titration treaters, be furnished with separately: pH electrode, Mettler, model DG 111 and luminosity electrode, Mettler, model DP 550
100 ml polypropylene titration beakers
150 milliliters of glass titration vessels with cover
The pressure filter of 100 milliliters of capacity
The nitrocellulose film filter, hole dimension 0.1 μ m, 47 mm
, Whatman(subscription number No. 7181-004 for example)
Reagent
CTAB(C
CTAB=0.015 mol, in deionized water) and NDSS(concentration=0.00423 mol, in deionized water) solution buy (Bernd Kraft GmbH with ready-made form, 47167 Duisburg: subscription number is the CTAB solution of No. 6056.4700, concentration 0.015 mol; Subscription number is the NDSS solution of No. 6057.4700,0.00423 mol), be stored in 25 ℃ and use in month.
Program
1. blank titration
Before each measurement series, should check the consumption of the NDSS solution that once is used for 5 milliliters of CTAB solution of titration every day.This is equivalent to 100% transparency by before the beginning titration luminosity electrode being set in 1000 ± 20 mV() get off to carry out.
Accurately, 5.00 milliliters of CTAB solution are inhaled moved on in the titration beaker and add 50.0 ml deionized water.By the measuring method that the technician is familiar with, use DL 55 titration treaters, under agitation carry out titration with NDSS solution, reach maximum turbidity until this solution.Determine consumption V in the NDSS solution of milliliter
AEach titration should be carried out in triplicate.
2. absorption
Use grinding machine (Krups, Model KM 75, Article No. 2030-70) making 10.0 gram moisture contents is that 5 ± 2% Powdered, sphere-like or particulate silica (if suitably, by in loft drier 105 ℃ of dryings or by the even wetting moisture content of regulating) size reduces 30 seconds.Accurately, the sample (initial mass E) that 500.0 milligrams of described sizes are reduced is transferred in 150 milliliters of titration vessels that have magnetic stirring bar and accurately is metered into 100.0 milliliters of CTAB solution (T
1).Stir maximum 1 minute of content until complete wetting with the closed with covers titration vessel and with Ultra Turrax T 25 agitators (stir shaft KV-18G, 18 mm dias) with 18 000rpm.Titration vessel is screwed onto on the DL 70 titration treaters and uses the KOH(0.1 mol) with the numerical value of pH regulator to 9 ± 0.05 of suspension.
Suspension in titration vessel in ultra sonic bath (Bandelin, Sonorex RK 106 S, 35 kHz, 100 W active power or 200 W peak powers) 25 ℃ of sonications 4 minutes.Immediately by film filter pressure filtration under 1.2 crust nitrogen pressure.Throw aside initial 5 milliliters of parts.
3. titration
5.00 milliliters of residual filtrate are inhaled to move on in 100 milliliters of titration beakers and with deionized water be supplemented to 50.00 milliliters.This titration beaker is screwed onto on the DL 55 titration treaters and under agitation with the titration of NDSS solution until reaching maximum turbidity.Determine consumption V in the NDSS solution of milliliter
BEach titration should be carried out in triplicate.
Calculate
V
A=be used for the NDSS solution consumption in milliliter of titration check sample
V
B=when using filtrate in the NDSS solution consumption of milliliter
C
CTAB=in the CTAB strength of solution of mol
M
CTAB=CTAB molar mass=364.46 gram/moles
T
1=in the CTAB solution addition of liter
The occupancy of P=CTAB=578.435 meters squared per gram
The initial mass of I=silicon-dioxide
Ctab surface is long-pending based on anhydride silica, therefore carries out following correction:
Measure the moisture content of silicon-dioxide according to described method " mensuration of moisture content ".
The mensuration that DBP absorbs
The following DBP that measures in based on the method for standard DIN 53601 absorbs (DBP value), and it is the criterion of the specific absorption of precipitated silica:
Powdered or the bead silicon-dioxide (if suitably, by regulate moisture content 105 ℃ of dryings in loft drier) of 12.50 gram 0-10% moisture contents is introduced the kneading chamber (system Article Number 279061) (the egress filtering device of nonwetting torsional moment converter) of Brabender Absorptometer " E ".Under the particulate situation, use 1 to 3.15 millimeter screen grading (from the stainless steel sift of Retsch) (using the plastics scraper particle to be pressed gently the sieve of 3.15 millimeters of via size).Mixing continuously under (the kneader blade is with the speed rotation of 125 rpm), using Brabender T 90/50 Dosimat in this mixture, dropwise to add dibutyl phthalate with the speed of 4 ml/min in room temperature.Its mixing of passing through is only mixed and is carried out with a small amount of power, and monitors by digital indicator.When finishing near mensuration, mixture becomes pasty state, and this shows as being increased sharply of required power.When indicating meter showed 600 numerals (0.6 Nm moment of torsion), electrical contact cut off kneader and DBP charging.The synchronous motor that the DBP charging is used is connected on the digital counter, so that the DBP that can read in milliliter consumes.
DBP absorbs with g/ (100 g) and is the unit report and uses following formula to calculate:
DBP=absorb wherein in the DBP of g/ (100 g)
V=consume in the DBP of milliliter
D=in the DBP density (is 1.047 grams per milliliters at 20 ℃) of grams per milliliter
I=in the silicon-dioxide initial mass of gram
C=from the correction value of moisture table of corrections, in g/ (100 g)
For anhydrous dried silica definition DBP absorbs.When using wet precipitated silica, calculate DBP and absorb the necessary correction value of considering
CCan determine this value by following table of corrections; For example, 5.8% silicon-dioxide water-content can mean increases by 33 g/ (100 g) for DBP absorbs.The moisture content of silicon-dioxide is measured according to " moisture content or drying loss are measured " method.
The moisture table of corrections of dibutyl phthalate absorption (anhydrous)
The mensuration of screenings (Ro-Tap)
This method is used to measure 300 microns of the relative coarse fractions (〉 stayed on the predetermined sieve) with relative fine fraction (＜75 microns).For the screenings analysis, testing sieve---in each case for 200 millimeters of sieve diameters, have different nominal sieve meshes, (DIN ISO 565 T.2) the analysis sieve made that has the metallic screen fabric---in sieve tray column, superpose each other with following order:
Screen tray, 75 microns, 150 microns, 300 microns
Sieve tray column is introduced the Tyler Ro-Tap B 8260 that has timing register with described order and is analyzed in the sieve apparatus, and the described silica dioxide granule of 100.00 gram homogeneous sample sizes is transferred on the sieve of the top.Be the homogenizing sample, it carefully mixed and be weighed into 100 ± 1 restraining in plastics bag.Sieve lid and guide cone (taper) are installed, and under circumferential motion and tapping campaign, sieved 5 minutes.After 5 minutes, the resistates on each sieve is weighed into 0.1 gram precision at vibrosieve.Use following formula calculation result:
Following mensuration screenings (Ro-Tap):
Sieve fraction (Ro-Tap,＜75 μ m)=(A in %
S/ E) * 100% and
Screenings (Ro-Tap,〉300 μ m in %)=(A
300/ E) * 100%,
Wherein
E=in the particle initial mass of gram
A
s=in the final quality on the screen tray of gram
A
300=in the final quality on 300 microns testing sieves of gram
By the determination of laser diffraction granularity
Use the determination of laser diffraction powder size be based on particle on all directions with the monochromatic phenomenon of varying strength figure scattering.Granularity is depended in this scattering.Particle is more little, and scattering angle is big more.
Specimen preparation and measurement (rinsing of module etc.) are carried out with complete deionization (DI) water under the situation of wetting ability precipitated silica, or carry out with straight alcohol under can not be fully by the situation of the precipitated silica of water-wet.
Before beginning measurement, with laser-diffractometer LS 230(Coulter) and liquid module (small volume module plus, 120 milliliters, Coulter) warming-up is 2 hours, this module is also calibrated for three times with the DI water rinse, under the situation of hydrophobic precipitated silicas, it uses ethanol rinsing three times.
In the control strip of instrument software, by menu item " measure (Measurement) " select File window " Calculate Opt. Model " and stipulate refractive index in the .rfd file: liquid refractive index B.I. real (real number)=1.332(is 1.359 for ethanol); Material refractive index real(real number)=1.46; The imaginary(imaginary number)=0.1; Shape factor 1.In addition, in this file window, select following items: (offset measurement) measured in biasing, regulate (adjustment), background is measured (background measurement), setting measurement concentration (set measurement conc.), input sample message (input sample info), input measurement information (input measurement info), Measuring Time (measuring time) 60 s, measure number of times (number of measurements) 1, no PIDS data (no PIDS data), size-grade distribution (size distribution).Pump speed on this instrument is set in 30%.
Use 2 milliliters of disposable volumetric pipettes, the unit for uniform suspension of 1 gram silicon-dioxide in 40 milliliters of DI water added in the liquid module of this instrument, to realize having the constant density and the instrument report " OK " of 8% to 12% photoabsorption.Measure in room temperature.By raw-data map, this software calculates size-grade distribution and d based on volume distributed median
50Value (intermediate value) wherein counts consideration with Mie theory and optical model parameter (.rfd file).
The mensuration of screenings (Alpine)
This mensuration of screenings is based on DIN ISO 8130-1, uses the air spray method of sieving of Alpine S 200 air spray screen devices.In order to measure particulate and particulate d
50Value comprises sieve mesh〉300 microns sieve.In order to measure d
50Value must be selected sieve so that they produce size-grade distribution, can measure d according to Fig. 2 thus
50Value.With with ISO 2591-1, chapters and sections 8.2 identical modes make the diagram and the evaluation and test.
d
50Value is meant the following particle diameter in the cumulative particle size distribution: it is d that the particle diameter of 50% particle is less than or equal to particle diameter
50The particle diameter of the particle of value.
The following example is intended to more sets forth in detail the present invention and does not limit its scope.
Embodiment
Embodiment 1
The 42 cubic metres of water of in the precipitation vessel of 90 cubic metres of capacity, packing into.Add 0.95 cubic metre of water glass (Na
2O content 6.1 weight %, SiO
2Content 20.7 weight %).Subsequently this initial charge is heated to 91.8 ℃.This initial charge is when the precipitation beginning, and the pH when promptly beginning to add water glass and sulfuric acid (about 98.0 ± 0.5 weight %) simultaneously in this initial charge is 10.3.Y value during the precipitation beginning is 5.3.After this, through 72 minutes and temperature keep constant down, add water glass (as above regulation) and sulfuric acid (as above regulation) so that the pH of precipitation when finishing be 9.99 and the Y value during the precipitation end be 4.85.After 72 minutes, stop to add water glass, further add sulfuric acid until reaching pH 4.7.After this this suspension was stirred 20 minutes at this pH.
Use the membrane filtration press to filter gained suspension, and wash filter cake with water.Solid content is that the filter cake of about 20 weight % liquefies in dissolver subsequently.Be that about 20 weight % and pH are about 5.8 silicon-dioxide feed spray drying so that the finished product have 6.2 the pH that records with 5% form of suspension subsequently with solid content.Subsequently should spray-dired product granulation by the roller tablets press.Carry out the roller granulation by two coarctate format rolls.Powder-product outgases by vacuum system (negative pressure 0.08 crust) under the situation of further not adding tackiness agent or liquid and evenly introduces between the roller of two-sided installation, positioned vertical.Under the pressure that speed of rotation and the 70-80 of 18-20 rpm cling to, pulverize the powder of this compacting by grinding mill (10 millimeters of sieve meshes).Fine fraction sifts out and sends back in the powder feed with vibratory screening apparatus (1 * 10 millimeter of sieve mesh).
The physical-chemical data of the representative sample of gained powder-product (embodiment 1a) and granulated product (embodiment 1b) is listed in the table 1.
Embodiment 2
The 40 cubic metres of water of in the precipitation vessel of 90 cubic metres of capacity, packing into.Add 1.27 cubic metres of water glass (Na
2O content 6.1%, SiO
2Content 20.5%).Subsequently this initial charge is heated to 87 ℃.This initial charge is when the precipitation beginning, and the pH when promptly beginning to add water glass and sulfuric acid (about 98.0 ± 0.5 weight %) simultaneously in this initial charge is 10.5.Y value during the precipitation beginning is 6.6.After this, through 90 minutes and temperature keep constant down, add water glass (as above regulation) and sulfuric acid (as above regulation) so that the pH of precipitation when finishing be 9.9 and the Y value during the precipitation end be 6.6.After 90 minutes, stop to add water glass, further add sulfuric acid until reaching pH 4.5.After this this suspension was stirred 30 minutes at this pH.
Use the membrane filtration press to filter gained suspension, and wash filter cake with water.Solid content is that the filter cake of about 20 weight % liquefies in dissolver subsequently.Be that about 20 weight % and pH are about 5.8 silicon-dioxide feed spray drying subsequently with solid content, so that by in the drying operation that is metered under the situation of ammonia, the finished product have 6.2 the pH that records with 5% form of suspension.Subsequently should spray-dired product granulation by the roller tablets press.Carry out the roller granulation by two coarctate format rolls.Powder-product outgases by vacuum system (negative pressure 0.08 crust) under the situation of further not adding tackiness agent or liquid and evenly introduces between the roller of two-sided installation, positioned vertical.Under the pressure that speed of rotation and the 70-80 of 18-20 rpm cling to, pulverize the powder of this compacting by grinding mill (10 millimeters of sieve meshes).Fine fraction sifts out and sends back in the powder feed with vibratory screening apparatus (1 * 10 millimeter of sieve mesh).
The physical-chemical data of the representative sample of gained powder-product (embodiment 2a) and granulated product (embodiment 2b) is listed in the table 1.
Embodiment 3
The 40 cubic metres of water of in the precipitation vessel of 90 cubic metres of capacity, packing into.Add 1.26 cubic metres of water glass (Na
2O content 6.3, SiO
2Content 21.4).Subsequently this initial charge is heated to 84 ℃.This initial charge is when the precipitation beginning, and the pH when promptly beginning to add water glass and sulfuric acid (about 98.0 ± 0.5 weight %) simultaneously in this initial charge is 10.5.Y value during the precipitation beginning is 6.6.After this, through 90 minutes and temperature keep constant down, add water glass (as above regulation) and sulfuric acid (as above regulation) so that the pH of precipitation when finishing be 9.9 and the Y value during the precipitation end be 6.2.After 90 minutes, stop to add water glass, further add sulfuric acid until reaching pH 4.0.After this this suspension was stirred 30 minutes at this pH.
Use the membrane filtration press to filter gained suspension, and wash filter cake with water.Solid content is that the filter cake of about 20 weight % liquefies in dissolver subsequently.Be that about 20 weight % and pH are about 5.8 silicon-dioxide feed spray drying so that the finished product have 6.2 the pH that records with 5% form of suspension subsequently with solid content.Subsequently should spray-dired product granulation by the roller tablets press.Carry out the roller granulation by two coarctate format rolls.Powder-product outgases by vacuum system (negative pressure 0.08 crust) under the situation of further not adding tackiness agent or liquid and evenly introduces between the roller of two-sided installation, positioned vertical.Under the pressure that speed of rotation and the 70-80 of 18-20 rpm cling to, pulverize the powder of this compacting by grinding mill (10 millimeters of sieve meshes).Fine fraction sifts out and sends back in the powder feed with vibratory screening apparatus (1 * 10 millimeter of sieve mesh).
The physical-chemical data of the representative sample of gained powder-product (embodiment 3a) and granulated product (embodiment 3b) is listed in the table 1.
Table 1
。
Claims (13)
1. prepare the method for precipitated silica, it comprises the following steps:
A) initial charge of the aqueous solution of preparation water or alkalimetal silicate and/or alkaline earth metal silicate,
B) at 80 to 100 ℃, alkalimetal silicate and/or alkaline earth metal silicate and souring agent metering are simultaneously under agitation added in this initial charge,
C) will precipitate suspension and be acidified to 2.5 to 6.0 pH again,
D) filter, wash and drying,
It is characterized in that step a) and/or b) in used described alkalimetal silicate and/or alkaline earth metal silicate alkalimetal oxide and/or the dioxide-containing silica of alkaline earth metal oxide content and 14 weight % to 23 weight % with 4 weight % to 7 weight %, be characterised in that step b) and/or c) in used souring agent be that to be selected from by concentration be that sulfuric acid, the concentration of 90 weight % to 98.5 weight % is that hydrochloric acid, the concentration of 34 weight % to 42.7 weight % is that nitric acid, the concentration of 60 weight % to 68 weight % is phosphoric acid, carbonic acid or the CO of 80 weight % to 100 weight %
2, and sodium bisulfite or SO
2The souring agent of the group of forming, and the pH(when being characterised in that based on the precipitation beginning records at 60 ℃), the pH(of described precipitation suspension records at 60 ℃) in precipitation process, reduce by 1% to 20%.
2. according to the method for claim 1,
It is characterized in that
At step c) and d) between gained suspension was stirred 1 to 90 minute after 60 to 100 ℃.
3. according to the method for claim 1 or 2,
It is characterized in that
This alkalimetal silicate and/or alkaline earth metal silicate have 2.5 to 4.5 modulus.
4. according to each method of claim 1 to 3,
It is characterized in that
This alkalimetal silicate is water glass or potassium silicate.
5. according to each method of claim 1 to 4,
It is characterized in that
PH reduces by 3% to 10% in precipitation process.
6. according to each method of claim 1 to 5,
It is characterized in that
PH is 8 to 12 when the precipitation beginning and is 6.5 to 11 when precipitation finishes.
7. according to each method of claim 1 to 6,
It is characterized in that
Y value during based on the precipitation beginning, the concentration of alkalimetal ion in the described reaction soln---with Y value representation---reduces maximum 25% in precipitation process.
8. according to the method for claim 7,
It is characterized in that
The concentration of alkalimetal ion in the described reaction soln---with Y value representation---is 3 to 6 when the precipitation beginning.
9. according to the method for claim 7,
It is characterized in that
The concentration of alkalimetal ion in the described reaction soln---with Y value representation---is 6 to 8 when the precipitation beginning.
10. according to each method of claim 1 to 9,
It is characterized in that
The described time length of adding silicate solutions and souring agent simultaneously is 50 to 80 minutes or 80 to 120 minutes.
11. according to each method of claim 1 to 10,
It is characterized in that
Described add silicate solutions and souring agent simultaneously before or among add ionogen.
12. can be by the precipitated silica that obtains according to each method of claim 1 to 11.
13. can be by the precipitated silica that obtains according to each method of claim 1 to 11 purposes as the filler in the following product: pneumatic tyre, summer with tire, winter with tire and annual tyre surface, tyres for passenger cars with tire, the MPV tire, motorcycle tyre, carcass parts, cable sheath, flexible pipe, rotating band, travelling belt, roll cladding thing, sole, packing ring and damping element.
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|---|---|---|---|
| PCT/CN2008/001556 WO2010022544A1 (en) | 2008-09-01 | 2008-09-01 | Process for preparing precipitated silicas, precipitated silicas and their use |
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| CN104066683A (en) * | 2012-01-25 | 2014-09-24 | 罗地亚运作公司 | Precipitated-silica production method |
| CN104080736A (en) * | 2012-01-25 | 2014-10-01 | 罗地亚运作公司 | Precipitated-silica production method |
| CN104114491A (en) * | 2011-12-23 | 2014-10-22 | 罗地亚运作公司 | Precipitated-silica production method |
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| FR2962996B1 (en) | 2010-07-23 | 2012-07-27 | Rhodia Operations | NEW PROCESS FOR THE PREPARATION OF PRECIPITED SILICES |
| JP5868520B2 (en) * | 2011-12-23 | 2016-02-24 | ローディア オペレーションズ | Method for producing precipitated silica |
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Citations (1)
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| CN1927712A (en) * | 2005-09-09 | 2007-03-14 | 德古萨公司 | Precipitated silicas with particular pore size distribution |
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| DE10151777A1 (en) * | 2001-10-19 | 2003-08-07 | Degussa | Precipitated silica for use, e.g., in tires, battery separators or anti-blocking agents is produced in Taylor reactor fed with aqueous silicate solution and acidifying agent |
| EP1577263A4 (en) * | 2002-07-10 | 2010-04-14 | Tokuyama Corp | Cake of easily dispersible precipitated silica and process for producing the same |
| BRPI0406904A (en) * | 2003-01-22 | 2005-12-13 | Degussa | specially precipitated silicic acids for rubber applications |
| CN1903720B (en) * | 2005-07-26 | 2010-05-05 | 山西师鸣精细化工有限公司 | One step process of preparing precipitated silicon dioxide using high concentration sulfuric acid |
| DE102005043201A1 (en) * | 2005-09-09 | 2007-03-15 | Degussa Ag | Precipitated silicas with a special pore size distribution |
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| CN104114491B (en) * | 2011-12-23 | 2017-03-08 | 罗地亚运作公司 | The method preparing precipitated silica |
| US9725325B2 (en) | 2011-12-23 | 2017-08-08 | Rhodia Operations | Process for preparing precipitated silicas |
| CN104066683A (en) * | 2012-01-25 | 2014-09-24 | 罗地亚运作公司 | Precipitated-silica production method |
| CN104080736A (en) * | 2012-01-25 | 2014-10-01 | 罗地亚运作公司 | Precipitated-silica production method |
| US9695053B2 (en) | 2012-01-25 | 2017-07-04 | Rhodia Operations | Process for preparing precipitated silica having specific morphology, particle size and porosity |
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