CN109368649B - Method for preparing precipitated white carbon black by improved dropwise adding process - Google Patents

Method for preparing precipitated white carbon black by improved dropwise adding process Download PDF

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CN109368649B
CN109368649B CN201811303474.8A CN201811303474A CN109368649B CN 109368649 B CN109368649 B CN 109368649B CN 201811303474 A CN201811303474 A CN 201811303474A CN 109368649 B CN109368649 B CN 109368649B
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reaction
spraying
water glass
controlling
sulfuric acid
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CN109368649A (en
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周敏
傅舟平
彭令军
唐任志
唐志凡
刘翠杰
姜大明
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Zhuzhou Xinglong New Material Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicon Compounds (AREA)

Abstract

The invention provides a method for preparing precipitated white carbon black by an improved dropwise adding process, which comprises the following steps: preparing a base solution in the reaction kettle and controlling the content of water glass; controlling the stirring speed and the reaction temperature according to different products to be generated, spraying sulfuric acid from the bottom of the reaction kettle, and simultaneously spraying a water glass solution from the bottom or the top of the reaction kettle, and reacting until the water glass solution is sprayed; after the temperature is raised, spraying sulfuric acid from the bottom of the reaction kettle again, controlling the pH value of the reaction system, acidifying and curing until the reaction is finished; and carrying out filter pressing, washing, slurrying and drying on the obtained synthetic liquid to obtain the precipitated white carbon black. Compared with the existing precipitation method, the method has the advantages that sulfuric acid is sprayed from the tank bottom, and the water glass solution is added into the prepared white carbon black with different specifications from the tank bottom or the tank top, so that the specific surface areas and oil absorption values of different white carbon black products can be improved; and in the production process, the tail gas emission is changed from acidic emission to neutral emission, so that the product quality can be effectively improved, a new product is developed, and the environment friendliness is completely realized.

Description

Method for preparing precipitated white carbon black by improved dropwise adding process
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for preparing precipitated silica by improving a dropping process.
Background
White carbon black is also called hydrated silicon dioxide, and the conventional production methods at present mainly comprise a gas phase method and a precipitation method. Wherein the white carbon black is mainly used as a reinforcing agent of silicon rubber, a coating and an unsaturated resin thickener, a reinforcing agent of natural rubber and synthetic rubber, a toothpaste friction agent and the like.
The precipitation method is to produce silicon dioxide by using sulfuric acid, hydrochloric acid, carbon dioxide and water glass as basic raw materials. The precipitation method production process mainly adopts sulfuric acid and water glass as raw materials for production, and the white carbon black synthetic liquid obtained after reaction is a mixed system of silicon dioxide, sodium sulfate and water. The precipitation method is used for preparing the white carbon black product, different self-polymerization degrees among primary particles are formed in the synthesis process due to different dropwise adding characteristics of acid and alkali in a synthesis tank during reaction, and the different self-polymerization degrees form the white carbon black product with different particle size, specific surface area, dispersity, different structure degrees in rubber and other performances. The market application fields of the white carbon black products with different properties are different. CN101659415A adds silane coupling agent into water glass solution before reaction, then uses hydrochloric acid as precipitator to prepare precipitated silica, although the problem that silica particles are easy to agglomerate can be solved, the purity is affected, and the method is not suitable for reinforcing filler of rubber. CN14347000A proposes a method for preparing precipitated silica by a two-step method, in which an acidulant is added into water glass to react until the pH value of a medium is 7.0-9.2, and the rest acidulant and the water glass are introduced simultaneously under the condition of keeping the pH value unchanged to prepare silica powder. In addition, in the synthesis process of the white carbon black by the precipitation method, a certain amount of water vapor and acid gas are discharged because continuous dropwise adding is needed in the synthesis process of acid and alkali, so that the investment of environmental management and treatment is increased.
Therefore, a method for preparing white carbon black by effectively improving a precipitation method is urgently needed, the regulation and control intervals of different specification indexes of products are increased, the market application is expanded, the added value of the products is improved, and the environment friendliness and different market requirements are met.
Disclosure of Invention
Aiming at the technical problems in the related art, the invention provides a method for preparing precipitated silica by improving a dropping process, which can effectively improve the product quality, develop a new product, increase the regulation and control intervals of different specification indexes of the product and effectively meet the requirement of environmental friendliness.
In order to achieve the technical purpose, the technical scheme of the invention is realized as follows:
on one hand, the invention provides a method for preparing precipitated silica by improving a dropping process, which comprises the following steps:
1) adding process hot water into a reaction kettle, stirring and heating to a reaction temperature, dripping a water glass solution in advance, and controlling the content of water glass in a base solution to be 0.07 mol/L;
2) controlling the deviation of the reaction temperature to be +/-0.1 ℃ according to different required products, spraying sulfuric acid from the bottom of the reaction kettle at a speed of 0.6-0.9 cubic meter per hour, spraying a water glass solution from the bottom or the top of the reaction kettle at a speed of 12-14 cubic meters per hour, controlling the stirring speed to react until the spraying and the dropwise adding of the water glass solution are finished, and controlling the reaction time to be 90-100 min;
3) raising the temperature of the reaction system obtained in the step 2) by 5 ℃, changing the stirring speed, spraying sulfuric acid at the speed of 0.3-0.5 cubic meter/hour from the bottom of the reaction kettle after balancing, controlling the pH of the reaction system to be 4.3-4.8 at 1/2 of the speed in the step 2), and continuing stirring and curing after spraying is finished until the reaction is finished; wherein the weight ratio of the concentrated sulfuric acid sprayed in the step 2) to the concentrated sulfuric acid sprayed in the step 3) is 1: 0.5;
4) and (3) carrying out filter pressing, washing, slurrying and drying on the synthetic liquid to obtain the precipitated white carbon black.
Further, the volume usage of the base solution is 37-45% of the volume of the reaction kettle. Preferably 37%, 43% or 45%.
Furthermore, the amount of the process hot water in the base solution is 37-45 cubic (preferably 37 cubic, 43 cubic or 45 cubic), the amount of the water glass solution with the concentration of 2.2-2.8 mol/L is 1.2-1.5 cubic meters, and the volume ratio is 185: 6-172: 6, preparing a base solution with the water glass concentration of 0.07 mol/L. The process hot water may be of the type: soft water, pure water, deep well water, tap water, and optionally an electrolyte solution (e.g., Na)+Ionic salt solutions such as sodium chloride solutions).
Further, in the step 1), the water glass solution is 2.2-2.8 mol/L and is subjected to filtration and impurity removal.
Further, in the step 1), the stirring speed is 150-400 rpm.
Further, in the step 2), the reaction of controlling the stirring speed is adjusted according to different obtained products, and the specific conditions are as follows:
A) producing square meter with high specific surface area of 200-230 square meters per gram and high oil absorption of 2.6-2.7 cm3The reaction time is 100min for the product per gram, and the reaction temperature is 80 +/-0.1 DEG CControlling; regulating and controlling reaction required 12.45m3Spraying all the water glass reaction solution with the flow rate per hour into the kettle from the top of the kettle; stirring for 0-40 min at a stirring speed of 150 rpm; stirring for 40-100 min at a stirring speed of 400 rpm;
B) producing the low specific surface area square meter of 110 to 130 square meters per gram and the low oil absorption of 2.10 to 2.20cm3The reaction time is 90min and the reaction temperature is controlled according to 90 plus or minus 0.1 ℃ when per gram of the product; regulating and controlling reaction required 13.73m3Spraying all the water glass reaction solution into the kettle from the kettle bottom; stirring for 0-40 min at a stirring speed of 400 rpm; stirring for 40-90 min at a stirring speed of 150 rpm;
C) the production specific surface is 150-180 m2The oil absorption value of the oil absorption material is 2.35-2.45 cm3The reaction time is 100min when per gram of the product, and the reaction temperature is controlled according to 85 +/-0.1 ℃; regulating and controlling reaction required 12.45m3The water glass reaction solution is added into the reactor from the top and the bottom of the reactor at 6.225m respectively3Spraying the mixture into a kettle; stirring for 0-40 min at a stirring speed of 300 rpm; 40-100 min, and the stirring speed is 200 rpm.
Further, the sulfuric acid can be a flue gas production type, an ore production type and a sulfur production type, the concentration of the sulfuric acid is concentrated sulfuric acid and dilute sulfuric acid, and the sulfuric acid with the mass fraction of 10-98% can be used.
Further, in the step 2), the molar concentration of the water glass solution is 1.1-1.4 mol/L, the modulus is 3.2-3.6, and the iron content is within 150PPM or within 1000 PPM.
Further, the spraying is performed by adopting a spraying pipeline, the spraying pipeline can be manufactured according to the spraying flow, and the material of the spraying pipeline is an acid-resistant stainless steel pipe or an acid-resistant pressure-resistant tetrafluoro pipe.
Further, in the step 2), the spraying weight ratio of the concentrated sulfuric acid to the water glass solution is 0.07-0.1: 1, and the spraying amount of the concentrated sulfuric acid and the water glass solution is used for maintaining the concentration of hydroxide ions in the reaction system to be 0.06-0.08 mol/L.
Further, in step 3), the stirring speed was changed to 200 rpm.
Further, in the step 3), the balancing time is 5-10 minutes.
Further, in the step 3), the aging time is 30 minutes.
Further, in the step 4), after washing, the press filter material with the solid content of 20-30% and the sodium sulfate content of 0.6-1.5% is obtained.
Further, in the step 4), the drying can be performed by means of high-speed centrifugal spray drying, pressure spray drying, fluidized bed drying and the like, and the water content of the product obtained after drying is 5-7%.
On the other hand, the invention provides precipitated silica prepared by the method.
On the other hand, the invention provides rubber prepared by using the precipitated silica prepared by the invention.
The invention has the beneficial effects that:
the invention provides a method for preparing precipitated silica by improving a dropping process, which is characterized in that a process mode of spraying sulfuric acid into the bottom of a reaction kettle (reaction tank) and simultaneously spraying water glass solution into the reaction kettle from the bottom or the top according to the type of the produced silica is adopted, so that most of acid gas generated in the reaction process is dissolved in a reaction system, the emission of the acid gas generated by spraying the sulfuric acid from the top can be avoided, and the method is environment-friendly. The improved mode of the dripping process can be suitable for the synthesis process of various white carbon black varieties, can be used for producing homologous various white carbon black products, and meets the requirements of different customers on different performances.
By using the spraying and dripping mode, the self-polymerization degree of the primary particles of the white carbon black in the synthesis process can be effectively controlled, and products with different performance indexes can be stably obtained, and the specific advantages are as follows:
1) when the square meter with high specific surface area of 200-230 square meters per gram and high oil absorption of 2.6-2.7 cm is produced3For the product/g, the reaction time is controlled to 12.45m3The reaction liquid of water glass with flow rate/h is totally sprayed into the kettle from the top of the kettle, the sulfuric acid is totally sprayed into the kettle from the bottom of the kettle, the spraying and dripping mode can lead the specific surface area and the oil absorption value of the white carbon black to develop towards the increasing trend, and compared with the product produced by the old process technology of spraying acid on the top and spraying alkali on the bottom, the specific surface area of the white carbon black prepared by the invention can be increased by 10m2Above, the oil absorption value can be improved by 0.10-0.20 cm3/g。
2) When the low specific surface area square meter is produced, the square meter is 110-130 square meters per gram, and the low oil absorption is 2.10-2.20 cm3In terms of product/g, 13.73m are required for the reaction3The reaction liquid of the water glass is completely sprayed into the kettle from the bottom of the kettle, the sulfuric acid is also completely sprayed into the kettle from the bottom of the kettle, the spraying and dripping mode can lead the specific surface area and the oil absorption value of the white carbon black to develop towards the trend of reducing, and compared with the product produced by the old process technology of spraying acid on the top and spraying alkali on the bottom, the specific surface area of the white carbon black prepared by the invention can be reduced by 10m2Above, the oil absorption value can be reduced by 0.10-0.15 cm3/g。
3) When the specific surface area for production is 150-180 square meters per gram, 2.35-2.45 cm3Per g oil absorption value product, 12.45m is needed for reaction3The water glass reaction solution is added into the reactor from the top and the bottom of the reactor at 6.225m respectively3And the sulfuric acid is completely sprayed into the kettle from the bottom of the kettle, and compared with the product produced by the original old process technology of spraying acid from the top and spraying alkali from the bottom, the spraying and dripping mode can keep the specific surface area and the oil absorption value of the white carbon black almost unchanged.
The white carbon black prepared by the method can optimize index quality such as specific surface, oil absorption value and the like. After the rubber is added into rubber, the rubber can better adapt to the requirements of different customers on the optimization performances such as the relevant tensile strength, the wear resistance, the elongation and the like, and can better meet the needs of market segmentation.
The dripping process is improved by only installing an injection pipeline and adding a set of flow control valve bank in the reaction kettle and matching with a DCS system to control configuration without greatly improving reaction equipment. The investment is small, the flexibility of equipment modification is strong, and the method can be more suitable for industrial production.
The method can completely stop the emission of acid mist in the preparation process, effectively eliminates the influence of the acid mist on environmental factors, and has the synthetic emission acidity of 3.0-4.0 in the original process production through the test of the pH of the synthetic waste gas emission and the pH of 7.0-8.0 in the synthetic production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
The method for preparing precipitated white carbon black by improving the dropping process specifically comprises the following steps:
⑴ adding 37-45 cubic (preferably 37, 43 or 45 cubic) hot water (the hot water can be soft water, pure water, deep well water, tap water, or electrolyte solution (such as Na)+Ionic salt solutions such as sodium chloride solutions). ) Starting a synthesis reaction kettle for stirring, raising the temperature of a reaction base solution to 80-90 ℃ required by the reaction, gradually pre-dripping a water glass solution with the concentration adjusted to be (equivalent concentration) 2.2-2.8 mol/L, filtering and removing impurities, controlling the content of water glass in the base solution to be about 0.07mol/L, wherein the volume of the base solution is 37-45% (preferably 37%, 43% or 45%) of the volume of the synthesis reaction kettle;
⑵, controlling stirring speed, adding amount of hot water for synthesis, synthesis temperature, total synthesis time, and Na according to the type of product+The amount of ionic salt solution added. In the synthesis reaction process, sulfuric acid and a water glass solution are simultaneously dripped (the mass ratio of the sulfuric acid to the water glass solution is 0.07-0.1: 1), the synthesis reaction time is 90-100 minutes, and the dripping speed of the synthetic acid and alkali is controlled in the reaction time (the dripping flow rate of the sulfuric acid is kept in the synthesis reaction solution (OH)-) The concentration is 0.06-0.08 mol weight), and the reaction is completed by dropwise adding the set volume of the water glass. (in this process, the sulfuric acid species can be flue gas production typeThe concentration of the concentrated sulfuric acid and the dilute sulfuric acid is divided into concentrated sulfuric acid and dilute sulfuric acid; the water glass solution has a molar concentration of 1.1-1.4 mol/L, a modulus of 3.2-3.6 and an iron content within 150PPM or 1000 PPM. ) (the material of the injection pipeline is an acid-resistant stainless steel pipe or an acid-resistant pressure-resistant tetrafluoro pipe. ) The method comprises the following steps:
A) producing square meter with high specific surface area of 200-230 square meters per gram and high oil absorption of 2.6-2.7 cm3For the product per gram, the production time is 100 minutes, 45 cubic meters (accounting for 45 percent of the volume of the reaction kettle) of synthetic hot water is added, and the synthetic temperature is controlled according to 80 plus or minus 0.1 ℃; regulating and controlling reaction required 12.45m3The reaction liquid of water glass with flow rate per hour is totally sprayed into the kettle from the top of the kettle, and the sulfuric acid is totally sprayed into the kettle from the bottom of the kettle. The stirring speed was controlled at 150rpm from the start of the synthesis to the 40 th minute; starting from the 40 th minute to finishing the synthesis at the 100 th minute, and controlling at 400 rpm; acidification and maturation were controlled at 200rpm, respectively.
B) Producing the low specific surface area square meter of 110 to 130 square meters per gram and the low oil absorption of 2.10 to 2.20cm3In terms of product/g, the production time is 90 minutes, the adding amount of the synthetic hot water is 37 cubic (accounting for 37 percent of the volume of the reaction kettle), and Na+The adding amount of the ionic salt solution is 600kg, the synthesis temperature is controlled according to 90 +/-0.1 ℃, and 13.73m is required by the reaction3The reaction solution of water glass is completely sprayed into the kettle from the bottom of the kettle, and the sulfuric acid is also completely sprayed into the kettle from the bottom of the kettle. The stirring speed was controlled at 400rpm from the start of the synthesis to the 40 th minute; starting from the 40 th minute to finishing the synthesis at the 90 th minute, and controlling at 150 rpm; acidification and maturation were controlled at 200rpm, respectively.
C) Producing the specific surface area of 150-180 square meters per gram and the oil absorption value of 2.35-2.45 cm3When per g of the product, the production time is 100 minutes, the adding amount of the synthetic hot water is 43 cubic (accounting for 43 percent of the volume of the reaction kettle), the synthetic temperature is controlled according to 85 +/-0.1 ℃, and the reaction needs 12.45m3The water glass reaction solution is added into the reactor from the top and the bottom of the reactor at 6.225m respectively3And h, spraying into the kettle, and spraying all sulfuric acid into the kettle from the bottom of the kettle. The stirring speed was controlled at 300rpm from the start of the synthesis to the 40 th minute; starting from the 40 th minute to finishing the synthesis at the 100 th minute, and controlling at 200 rpm; acidification and maturation were controlled at 200rpm, respectively.
⑶, after finishing the dripping, controlling the temperature of the solution to rise by about 5 ℃, regulating and controlling the stirring speed according to the step (2), after 5-10 minutes, dripping sulfuric acid from a jet pipeline at the bottom of the tank again, controlling the flow rate to be 1/2 during the synthesis reaction, measuring and controlling the pH of the solution to be 4.3-4.8, finally stirring and curing the synthesis solution for 30 minutes, and completing the synthesis.
⑷, carrying out filter pressing and washing on the synthetic liquid obtained in the above process by using a liquid-solid separation plate-and-frame filter press to obtain filter pressing slurry with the solid content of 20-30% and the sulfate content of 0.6-1.5%, and sending the filter pressing slurry to a product drying section.
⑸, carrying out high-speed centrifugal spray drying, pressure spray drying, fluidized bed drying and other modes on the white carbon black slurry in the drying section to obtain a product with the water content of 5.0-7.0%.
Compared with the existing precipitation method, the method has the advantages that the specific surface area and the oil absorption value of different white carbon black products can be improved by adopting the white carbon black products with different specifications prepared by a preparation method of spraying sulfuric acid from the bottom of the tank and adding water glass solution from the bottom or the top of the tank. And the tail gas emission in the production process is determined from acidic emission and is converted into neutral emission, so that the environment-friendly effect is completely realized.
Example 1
The method for preparing precipitated white carbon black by improving the dropping process specifically comprises the following steps:
⑴, adding 37 cubic process hot water (soft water added with 600kg of sodium chloride electrolyte) into a white carbon black reaction kettle, starting the synthesis reaction kettle to stir at the stirring speed of 400rpm, raising the temperature of reaction base liquid to 90 +/-0.1 ℃ required by the reaction, gradually pre-dripping water glass solution with the concentration adjusted to 2.2mol/L and filtering to remove impurities, controlling the content of the water glass in the base liquid of the reaction kettle to be about 0.07mol/L, wherein the volume of the base liquid is 37 percent of the volume of the synthesis reaction kettle;
⑵, after the reaction starts, spraying the water glass solution at the speed of 13.73 cubic meters per hour from a spraying pipeline at the top of the reaction kettle, adding sulfuric acid at the speed of 0.6 cubic meters per hour from a spraying pipeline at the bottom of the reaction kettle, simultaneously dripping the sulfuric acid and the water glass solution (the mass ratio of the sulfuric acid to the water glass solution is 0.07-0.1: 1), wherein the spraying weight ratio of the concentrated sulfuric acid to the water glass solution is 0.07-0.1: 1, and the reaction time is 0-40 miWithin n, the stirring speed is controlled at 400 rpm; controlling the stirring speed to be 150rmp within 40-100 min; the dropping speed of the synthetic acid and the base was controlled during the reaction time (the dropping flow rate of the sulfuric acid was maintained in the synthetic reaction solution (OH)-) The concentration is 0.06-0.08 mol weight) until the set water glass solution is completely dripped and reacted. (in the process, the sulfuric acid is sulfur production type, the concentration is 98 percent concentrated sulfuric acid, the mole concentration of the water glass solution is 1.1mol/L, the modulus is 3.2-3.6, and the iron content is within 150PPM or 1000 PPM.) (the material of the injection pipeline is an acid-resistant stainless steel pipe or an acid-resistant pressure-resistant tetrafluoro pipe.)
⑶, after finishing the dripping, controlling the temperature of the solution to rise by about 5 ℃, after 5 to 10 minutes, spraying 98 percent sulfuric acid from a prepared spraying pipeline at the bottom of the tank at the speed of 0.3 to 0.5 cubic meter per hour, controlling the flow rate to be 1/2 during the synthesis reaction, controlling the stirring speed to be 200rpm, measuring and controlling the pH value of the solution to be 4.3 to 4.8, finally stirring and curing the synthesis solution at 200rpm for 30 minutes, and completing the synthesis.
⑷, carrying out filter pressing and washing on the synthetic liquid obtained in the above process by using a liquid-solid separation plate-and-frame filter press to obtain filter pressing slurry with the solid content of 20-30% and the sulfate content of 0.6-1.5%, and sending the filter pressing slurry to a product drying section.
⑸, carrying out high-speed centrifugal spray drying, pressure spray drying, fluidized bed drying and other modes on the white carbon black slurry in the drying section to obtain a product with the water content of 5.0-7.0%.
The specific surface area of the product obtained by the method is 110-130 m2The oil absorption value of the oil-absorbing resin is 2.10-2.20 cm3The total iron content of the iron-containing composite material is 100-150 PPM or 450-650 PPM, and the total iron content of the iron-containing composite material is 5.0-7.0 wt% and 0.6-1.5 wt% of sodium sulfate, 97.5-98.5 wt% of silicon dioxide dry basis and 5.0-7.0 wt% of water content.
Example 2
The method for preparing precipitated white carbon black by improving the dropping process specifically comprises the following steps:
⑴, adding 45 cubic process hot water (tap water) into a white carbon black reaction kettle, starting the synthesis reaction kettle to stir at a stirring speed of 150rpm, raising the temperature of a reaction base solution to 80 +/-0.1 ℃ required by the reaction, gradually pre-dripping a water glass solution with the concentration adjusted to 2.46mol/L and impurity filtered to control the content of the water glass in the base solution of the reaction kettle to be about 0.07mol/L, wherein the volume of the base solution is 45 percent of the volume of the synthesis reaction kettle;
⑵, after the reaction starts, spraying the water glass solution from a spraying pipeline at the top of the reaction kettle at the speed of 12.45 cubic meters per hour, adding the sulfuric acid from a spraying pipeline at the bottom of the reaction kettle at the speed of 0.8 cubic meters per hour, simultaneously dripping the sulfuric acid and the water glass solution (the mass ratio of the sulfuric acid to the water glass solution is 0.07-0.1: 1), controlling the spraying weight ratio of the concentrated sulfuric acid to the water glass solution at 0.07-0.1: 1, controlling the stirring speed at 150rpm within 0-40 min, controlling the stirring speed at 400rmp within 40-90 min, and controlling the dripping speed of the synthetic acid and the alkali within the reaction time (the dripping flow rate of the sulfuric acid is maintained in the synthetic reaction solution (OH)-) The concentration is 0.06-0.08 mol weight) until the set water glass solution is completely dripped and reacted. (in the process, the sulfuric acid is flue gas production type concentrated sulfuric acid with the concentration of 98%; the water glass solution has the molar concentration of 1.23mol/L, the modulus of 3.2-3.6 and the iron content within 1000 PPM.) (the injection pipeline material is an acid-resistant stainless steel pipe or an acid-resistant pressure-resistant tetrafluoro pipe.)
⑶, after finishing the dripping, controlling the temperature of the solution to rise by about 5 ℃, after 5 to 10 minutes, spraying 98 percent sulfuric acid from a prepared spraying pipeline at the bottom of the tank at the speed of 0.3 to 0.5 cubic meter per hour, controlling the flow rate to be 1/2 during the synthesis reaction, controlling the stirring speed to be 200rpm, measuring and controlling the pH value of the solution to be 4.3 to 4.8, finally stirring and curing the synthesis solution at 200rpm for 30 minutes, and completing the synthesis.
⑷, carrying out pressure filtration and washing on the synthetic liquid obtained in the above process by using a liquid-solid separation plate-and-frame filter press to obtain pressure filtration slurry with the solid content of 20-30% and the sulfate content of 1.2-1.5%, and sending the pressure filtration slurry to a product drying section.
⑸, carrying out high-speed centrifugal spray drying, pressure spray drying, fluidized bed drying and other modes on the white carbon black slurry in the drying section to obtain a product with the water content of 6.0-7.0%.
The specific surface area of the product obtained by the invention is 200 to230m2The oil absorption value of the oil-absorbing resin is 2.60-2.70 cm3The water content per gram is 1.2-1.5 wt% of sodium sulfate, 97.5-98.5 wt% of silicon dioxide dry basis, 6.0-7.0 wt% of water content and 450-650 PPM of iron content.
Example 3
The method for preparing precipitated white carbon black by improving the dropping process specifically comprises the following steps:
⑴, adding 43 cubic process hot water (pure water) into the white carbon black reaction kettle, starting the synthesis reaction kettle to stir at the stirring speed of 300rpm, raising the temperature of the reaction base liquid to 85 +/-0.1 ℃ required by the reaction, gradually pre-dripping the water glass solution with the concentration adjusted to 2.2mol/L and filtered to remove impurities, and controlling the water glass content in the base liquid of the reaction kettle to be about 0.07mol/L, wherein the volume of the base liquid is 43 percent of the volume of the synthesis reaction kettle;
⑵, after the reaction starts, spraying the water glass solution from the top and the bottom of the reaction kettle respectively by using a spraying pipeline at the speed of 6.225 cubic meters per hour, adding the sulfuric acid from a spraying pipeline at the bottom of the kettle at the speed of 0.7 cubic meters per hour, dripping the sulfuric acid and the water glass solution simultaneously (the mass ratio of the sulfuric acid to the water glass solution is 0.07-0.1: 1), controlling the spraying weight ratio of the concentrated sulfuric acid to the water glass solution at 0.07-0.1: 1, controlling the stirring speed at 300rpm within 40-100 min within 0-40 min of the reaction time, controlling the stirring speed at 200rmp, and controlling the dripping speed of the synthetic acid and the alkali within the reaction time (the dripping flow rate of the sulfuric acid is maintained in the synthetic reaction solution (OH)-) The concentration is 0.06-0.08 mol weight) until the set water glass solution is completely dripped and reacted. (in the process, the sulfuric acid is sulfur production type, the concentration is 98 percent concentrated sulfuric acid, the water glass solution molar concentration is 1.1mol/L, the modulus is 3.2-3.6, and the iron content is less than 150 PPM.) (the injection pipeline material is an acid-resistant stainless steel pipe or an acid-resistant pressure-resistant tetrafluoro pipe.)
⑶, after finishing the dripping, controlling the temperature of the solution to rise by about 5 ℃, after 5 to 10 minutes, spraying 98 percent sulfuric acid from a prepared spraying pipeline at the bottom of the tank at the speed of 0.3 to 0.5 cubic meter per hour, controlling the flow rate to be 1/2 during the synthesis reaction, controlling the stirring speed to be 200rpm, measuring and controlling the pH value of the solution to be 4.3 to 4.8, finally stirring and curing the synthesis solution at 200rpm for 30 minutes, and completing the synthesis.
⑷, carrying out filter pressing and washing on the synthetic liquid obtained in the above process by using a liquid-solid separation plate-and-frame filter press to obtain filter pressing slurry with the solid content of 20-30% and the sulfate content of 0.6-0.8%, and sending the filter pressing slurry to a product drying section.
⑸, carrying out high-speed centrifugal spray drying, pressure spray drying, fluidized bed drying and other modes on the white carbon black slurry in the drying section to obtain a product with the water content of 5.0-6.0%.
The specific surface area of the product obtained by the method is 150-180 m2The oil absorption value of the oil-absorbing material is 2.35-2.45 cm3The water content per gram is 0.6-0.8 wt% of sodium sulfate, 98.0-99.0 wt% of dry silica, 5.0-6.0 wt% of water content and 100-150 PPM of iron content.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A method for preparing precipitated silica by an improved dropwise adding process is characterized by comprising the following steps:
1) adding process hot water into a reaction kettle, stirring and heating to a reaction temperature, dripping a water glass solution in advance, and controlling the content of water glass in a base solution to be 0.07 mol/L;
2) controlling the deviation of the reaction temperature to be +/-0.1 ℃ according to different required products, spraying sulfuric acid from the bottom of the reaction kettle at a speed of 0.6-0.9 cubic meter per hour, spraying a water glass solution from the bottom or the top of the reaction kettle at a speed of 12-14 cubic meters per hour, controlling the stirring speed to react until the spraying and the dropwise adding of the water glass solution are finished, and controlling the reaction time to be 90-100 min;
3) raising the temperature of the reaction system obtained in the step 2) by 5 ℃, changing the stirring speed, spraying sulfuric acid at the speed of 0.3-0.5 cubic meter/hour from the bottom of the reaction kettle after balancing, controlling the pH of the reaction system to be 4.3-4.8 at 1/2 of the speed in the step 2), and continuing stirring and curing after spraying is finished until the reaction is finished; wherein the weight ratio of the sulfuric acid sprayed in the step 2) to the sulfuric acid sprayed in the step 3) is 1: 0.5;
4) and (3) carrying out filter pressing, washing, slurrying and drying on the synthetic liquid to obtain the precipitated white carbon black.
2. The method for preparing precipitated silica by using the improved dropwise adding process according to claim 1, wherein in the step 1), the volume of the base solution is 37-45% of the volume of the reaction kettle; the water glass solution is 2.2-2.8 mol/L and is subjected to filtration and impurity removal.
3. The method for preparing precipitated silica according to claim 1, wherein in the step 2), the reaction of controlling the stirring speed is adjusted according to different products, specifically:
A) producing square meter with high specific surface area of 200-230 square meters per gram and high oil absorption of 2.6-2.7 cm3The reaction time is 100min and the reaction temperature is controlled according to 80 plus or minus 0.1 ℃ when the product is produced; regulating and controlling reaction required 12.45m3Spraying all the water glass reaction solution with the flow rate per hour into the kettle from the top of the kettle; stirring for 0-40 min at a stirring speed of 150 rpm; stirring for 40-100 min at a stirring speed of 400 rpm;
B) producing the low specific surface area square meter of 110 to 130 square meters per gram and the low oil absorption of 2.10 to 2.20cm3The reaction time is 90min and the reaction temperature is controlled according to 90 plus or minus 0.1 ℃ when per gram of the product; regulating and controlling reaction required 13.73m3Spraying all the water glass reaction solution into the kettle from the kettle bottom; stirring for 0-40 min at a stirring speed of 400 rpm; stirring for 40-90 min at a stirring speed of 150 rpm;
C) producing the specific surface area of 150 to 180 square meters per gram and the oil absorption value of 2.35 to 2.45cm3The reaction time is 100min when per gram of the product, and the reaction temperature is controlled according to 85 +/-0.1 ℃; regulating and controlling reaction required 12.45m3The water glass reaction solution is added into the reactor from the top and the bottom of the reactor at 6.225m respectively3Spraying the mixture into a kettle; stirring for 0-40 min at a stirring speed of 300 rpm; 40-100 min, and the stirring speed is 200 rpm.
4. The method for preparing precipitated silica according to claim 3, wherein in the step 2), the water glass solution has a molar concentration of 1.1-1.4 mol/L, a modulus of 3.2-3.6 and an iron content of less than 1000 ppm.
5. The method for preparing precipitated silica according to claim 4, wherein the spraying is performed by using a spraying pipeline; the spraying pipeline is manufactured according to spraying flow, and the material of the spraying pipeline is an acid-resistant stainless steel pipe or an acid-resistant pressure-resistant tetrafluoro pipe;
in the step 2), the spraying weight ratio of the sulfuric acid to the water glass solution is 0.07-0.1: 1, and the spraying amount of the sulfuric acid to the water glass solution is used for maintaining the concentration of hydroxide ions in a reaction system to be 0.06-0.08 mol/L.
6. The method for preparing precipitated silica by using the improved dropwise adding process according to claim 1, wherein in the step 3), the balancing time is 5-10 minutes; the stirring speed is changed to 200 rmp;
the aging time was 30 minutes.
7. The method for preparing precipitated silica according to claim 1, wherein in the step 4), the press filter material with a solid content of 20-30% and a sodium sulfate content of 0.6-1.5% is obtained after washing.
8. The method for preparing precipitated silica by using the improved dropwise adding process according to claim 7, wherein in the step 4), the drying is performed by adopting a high-speed centrifugal spray drying, pressure spray drying or fluidized bed drying mode, and the water content of the dried product is 5-7%.
9. Precipitated silica prepared by the method of any one of claims 1 to 8.
10. Rubber prepared by using the precipitated silica prepared by the method of any one of claims 1 to 8 as a raw material.
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