WO2023035098A1 - Method for preparing white carbon black for reinforcement and use thereof - Google Patents

Method for preparing white carbon black for reinforcement and use thereof Download PDF

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Publication number
WO2023035098A1
WO2023035098A1 PCT/CN2021/116856 CN2021116856W WO2023035098A1 WO 2023035098 A1 WO2023035098 A1 WO 2023035098A1 CN 2021116856 W CN2021116856 W CN 2021116856W WO 2023035098 A1 WO2023035098 A1 WO 2023035098A1
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Prior art keywords
treatment
preparation
carbon black
white carbon
reinforcement
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PCT/CN2021/116856
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French (fr)
Chinese (zh)
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陈南飞
卢爱平
王明贺
陈辰
陈家树
史彤
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无锡恒诚硅业有限公司
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Priority to PCT/CN2021/116856 priority Critical patent/WO2023035098A1/en
Priority to CN202180002655.0A priority patent/CN113924271B/en
Publication of WO2023035098A1 publication Critical patent/WO2023035098A1/en

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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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present application relates to the field of white carbon black, in particular to a preparation method and application of white carbon black for reinforcement.
  • silica is widely used in various fields due to its good specific surface properties, and the preparation method of silica has obvious influence on its properties.
  • CN107140643A is a kind of preparation method of high-strength and easily dispersible white carbon black, it uses fluosilicic acid as silicon raw material, is ammoniation agent step by step to carry out ammoniation reaction with gas ammonia, and in the second ammoniation reaction With the addition of dispersant, the prepared white carbon black is easy to disperse and has high reinforcing performance.
  • CN1337355A discloses a method for producing high-reinforcing white carbon black by ammoniating sodium fluorosilicate.
  • the specific surface area of white carbon black obtained by the current process method is low, and the transparency and reinforcement in rubber compounds are poor, so it is difficult to be used as high-reinforcing white carbon black. Strong white carbon black is used, and the process is long and the production cost is high.
  • a Na 2 SiF 6 step-by-step ammoniation treatment process is proposed. Firstly, the total amount of 25-50% Na 2 SiF 6 and 5-20% ammonia water are reacted at 30-45°C, which is beneficial to the tiny glue core.
  • the product of this application can be adjusted within the range of 130-220m 2 /g, and the DBP oil absorption value can be adjusted within the range of 2.0-3.3.
  • the product can be used as a reinforcing material for shoemaking and tires.
  • the current white carbon black for reinforcement still has problems such as poor reinforcement performance and small specific surface area.
  • This application provides a preparation method and application of white carbon black for reinforcement. Through the adjustment of the process in the preparation process, the poor reinforcing performance and small specific surface area of the white carbon black for reinforcement prepared by the current process are solved. The problem.
  • the application provides a method for preparing white carbon black for reinforcement, the preparation method comprising the steps of:
  • step (2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
  • the first treatment liquid includes chloroacetic acid and ammonium citrate
  • the second treatment liquid includes hydrochloric acid and acetic acid.
  • the scheme provided by this application realizes the preparation of high-performance white carbon black through the design of the preparation process and multiple treatments with a specific composition, and the specific surface area of the prepared white carbon black can reach 200-230cm 2 /g At the same time, the reinforcing performance of silica when used as a reinforcing material is significantly improved, and the mechanical properties of rubber products after reinforcement have achieved a good improvement.
  • the combination of chloroacetic acid and ammonium citrate is used in the first treatment to pretreat the water glass solution to provide a good environment for the second treatment, and then high-performance white carbon can be directly obtained under the treatment of hydrochloric acid and acetic acid Black product, when used as a reinforcing material, the mechanical properties of the reinforced material are greatly improved.
  • the introduction of ammonium citrate can regulate the precipitation rate of silica and then reduce the content of impurity elements in the product
  • a specific combination of hydrochloric acid and acetic acid is used to reduce the amount of silica produced under an ammonia atmosphere. The aggregation between the particles ensures that the obtained silica has good dispersibility.
  • the modulus of the water glass solution described in step (1) is 1.5-2, such as can be 1.5, 1.6, 1.7, 1.8, 1.9 or 2, etc., but not limited to the numerical values listed, the Other unrecited combinations within the scope are also applicable.
  • the mol ratio of chloroacetic acid and ammonium citrate in the first treatment liquid described in step (1) is 1:(0.3-0.5), such as 1:0.3, 1:0.31, 1:0. 0.32, 1:0.33, 1:0.34, 1:0.35, 1:0.36, 1:0.37, 1:0.38, 1:0.39, 1:0.4, 1:0.41, 1:0.42, 1:0.43, 1:0.44, 1:0.45, 1:0.46, 1:0.47, 1:0.48, 1:0.49 or 1:0.5, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the volume ratio of the water glass solution and the first treatment liquid in step (1) is 1:(2-3), such as 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9 or 1:3, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the first treatment in step (1) is carried out under a protective atmosphere.
  • the gas in the protective atmosphere includes carbon dioxide gas.
  • the first treatment can control the hydrolysis speed of silicon element in the solution under the protective atmosphere of carbon dioxide gas, and at the same time cooperate with the treatment liquid to make the liquid phase reach a good liquid phase condition after the first treatment of the liquid phase, which is the next second treatment.
  • a good foundation is laid and the pre-precipitation of silicon in the liquid phase is realized.
  • the volume content of carbon dioxide gas in the protective atmosphere is 2-7%, such as 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8% %, 4%, 4.2%, 4.4%, 4.6%, 4.8%, 5%, 5.2%, 5.4%, 5.6%, 5.8%, 6%, 6.2%, 6.4%, 6.6%, 6.8% or 7%, etc. , but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the remaining gas volume can be made up with other inert components, such as nitrogen, helium or argon.
  • the temperature of the first treatment in step (1) is 70-90°C, for example, it can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C °C, 78 °C, 79 °C, 80 °C, 81 °C, 82 °C, 83 °C, 84 °C, 85 °C, 86 °C, 87 °C, 88 °C, 89 °C or 90 °C, etc., but not limited to the listed values, Other unrecited combinations within this range are also applicable.
  • the first treatment time in step (1) is 70-90min, for example, 70min, 71min, 72min, 73min, 74min, 75min, 76min, 77min, 78min, 79min, 80min, 81min, 82min, 83min, 84min, 85min, 86min, 87min, 88min, 89min or 90min, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the volume ratio of the slurry and the second treatment liquid in step (2) is 1:(1.2-1.5), such as 1:1.2, 1:1.21, 1:1.22, 1 :1.23, 1:1.24, 1:1.25, 1:1.26, 1:1.27, 1:1.28, 1:1.29, 1:1.3, 1:1.31, 1:1.32, 1:1.33, 1:1.34, 1:1.35 , 1:1.36, 1:1.38, 1:1.4, 1:1.42, 1:1.44, 1:1.46, 1:1.48 or 1:1.5, etc., but not limited to the listed values, other unlisted combinations The same applies.
  • the molar ratio of hydrochloric acid and acetic acid in the second treatment liquid described in step (2) is 1:(1.2-1.5), such as can be 1:1.2, 1:1.21, 1:1.22, 1:1.23, 1: 1.24, 1:1.25, 1:1.26, 1:1.27, 1:1.28, 1:1.29, 1:1.3, 1:1.31, 1:1.32, 1:1.33, 1:1.34, 1:1.35, 1:1.36, 1:1.38, 1:1.4, 1:1.42, 1:1.44, 1:1.46, 1:1.48 or 1:1.5, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the second treatment in step (2) is carried out under an ammonia atmosphere.
  • the content of ammonia in the ammonia atmosphere is 25-30%, such as 25%, 25.2%, 25.4%, 25.6%, 25.8%, 26%, 26.2%, 26.4%, 26.8%, 27% %, 27.2%, 27.4%, 27.6%, 27.8%, 28%, 28.2%, 28.4%, 28.6%, 28.8%, 29%, 29.2%, 29.4%, 29.6%, 29.8% or 30%, etc., but not Limited to the listed values, other unlisted combinations within this range are also applicable.
  • the remaining gas volume can be made up with other inert components, such as nitrogen, helium or argon.
  • the introduction of ammonia gas atmosphere in the second treatment ensures that the silica formed in the second treatment has a good structure, avoids the aggregation of silica, and ensures that the prepared Silica has good dispersion performance and specific surface area.
  • the temperature of the second treatment in step (2) is 120-150°C, for example, it can be 120°C, 122°C, 124°C, 126°C, 128°C, 130°C, 132°C, 134°C °C, 136 °C, 138 °C, 140 °C, 142 °C, 144 °C, 146 °C, 148 °C or 150 °C, etc., but not limited to the listed values, and other unlisted combinations within this range are also applicable.
  • the time for the second treatment in step (2) is 30-45min, such as 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min, 40min, 41min, 42min, 43min, 44min or 45min, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the preparation method includes the following steps:
  • step (2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
  • the modulus of the water glass solution described in step (1) is 1.5-2;
  • the first treatment solution includes chloroacetic acid and ammonium citrate;
  • the mol ratio of chloroacetic acid and ammonium citrate in the first treatment solution is 1:(0.3-0.5);
  • the volume ratio of the water glass solution and the first treatment liquid is 1:(2-3);
  • the first treatment is carried out under a protective atmosphere;
  • the gas of the protective atmosphere includes Carbon dioxide gas;
  • the volume content of carbon dioxide gas in the protective atmosphere is 2-7%;
  • the temperature of the first treatment is 70-90°C;
  • the time of the first treatment is 70-90min;
  • the volume ratio of the slurry and the second treatment solution in step (2) is 1:(1.2-1.5); the second treatment solution includes hydrochloric acid and acetic acid; the mol ratio of hydrochloric acid and acetic acid in the second treatment solution It is 1: (1.2-1.5); the second treatment is carried out under an ammonia atmosphere; the content of ammonia in the ammonia atmosphere is 25-30%; the temperature of the second treatment is 120-150°C; The time of the second treatment is 30-45min.
  • the present application provides the application of the white carbon black for reinforcement obtained by the preparation method described in the first aspect, and the white carbon black for reinforcement is used for reinforcing rubber products.
  • the scheme provided by this application realizes the preparation of high-performance white carbon black through the design of the preparation process and multiple treatments with specific compositions, and the specific surface area of the prepared white carbon black can reach 200-230cm 2 /g, and at the same time, the reinforcing performance of silica when used as a reinforcing material is significantly improved, and the mechanical properties of rubber products after reinforcement have achieved a good improvement.
  • the reinforcement performance of the obtained silica is further enhanced by introducing specific atmosphere assistance in the multiple treatment processes.
  • the hardness JIS can reach more than 90
  • the tensile strength can reach more than 18.2MPa
  • the elongation can reach more than 660.5%.
  • This embodiment provides a preparation method of white carbon black for reinforcement, the preparation method comprising the following steps:
  • step (2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
  • the modulus of the described water glass solution of step (1) is 1.7; Described the first processing liquid comprises chloroacetic acid and ammonium citrate; The mol ratio of chloroacetic acid and ammonium citrate is 1:0.4 in the described first processing liquid; The volume ratio of the water glass solution and the first treatment liquid is 1:2.5; the first treatment is carried out under a protective atmosphere; the gas of the protective atmosphere includes carbon dioxide gas; the volume of carbon dioxide gas in the protective atmosphere The content is 4%; the temperature of the first treatment is 80°C; the time of the first treatment is 80min;
  • the volume ratio of the slurry and the second treatment solution in step (2) is 1:1.35; the second treatment solution includes hydrochloric acid and acetic acid; the molar ratio of hydrochloric acid and acetic acid in the second treatment solution is 1:1.35
  • the second treatment is carried out under an ammonia atmosphere; the content of ammonia in the ammonia atmosphere is 27%; the temperature of the second treatment is 130° C.; the time of the second treatment is 37 minutes.
  • This embodiment provides a preparation method of white carbon black for reinforcement, the preparation method comprising the following steps:
  • step (2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
  • the modulus of the described water glass solution of step (1) is 2; Described the first processing liquid comprises chloroacetic acid and ammonium citrate; The mol ratio of chloroacetic acid and ammonium citrate is 1:0.5 in the described first processing liquid; The volume ratio of the water glass solution and the first treatment liquid is 1:2; the first treatment is carried out under a protective atmosphere; the gas of the protective atmosphere includes carbon dioxide gas; the volume of carbon dioxide gas in the protective atmosphere The content is 2%; the temperature of the first treatment is 70°C; the time of the first treatment is 90min;
  • the volume ratio of the slurry and the second treatment solution in step (2) is 1:1.5; the second treatment solution includes hydrochloric acid and acetic acid; the molar ratio of hydrochloric acid and acetic acid in the second treatment solution is 1:1.2 ;
  • the second treatment is carried out under an ammonia atmosphere; the content of ammonia in the ammonia atmosphere is 25%; the temperature of the second treatment is 150° C.; the time of the second treatment is 45 minutes.
  • This embodiment provides a preparation method of white carbon black for reinforcement, the preparation method comprising the following steps:
  • step (2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
  • the modulus of the described water glass solution of step (1) is 1.5; Described the first processing liquid comprises chloroacetic acid and ammonium citrate; The mol ratio of chloroacetic acid and ammonium citrate is 1:0.5 in the described first processing liquid; The volume ratio of the water glass solution and the first treatment liquid is 1:3; the first treatment is carried out under a protective atmosphere; the gas of the protective atmosphere includes carbon dioxide gas; the volume of carbon dioxide gas in the protective atmosphere The content is 7%; the temperature of the first treatment is 90°C; the time of the first treatment is 70min;
  • the volume ratio of the slurry and the second treatment solution in step (2) is 1:1.2; the second treatment solution includes hydrochloric acid and acetic acid; the molar ratio of hydrochloric acid and acetic acid in the second treatment solution is 1:1.5 ;
  • the second treatment is carried out under an ammonia atmosphere; the content of ammonia in the ammonia atmosphere is 30%; the temperature of the second treatment is 120° C.; the time of the second treatment is 30 minutes.
  • This embodiment provides a preparation method of white carbon black for reinforcement, the preparation method comprising the following steps:
  • step (2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
  • the modulus of the described water glass solution of step (1) is 1.85; Described the first processing liquid comprises chloroacetic acid and ammonium citrate; The mol ratio of chloroacetic acid and ammonium citrate is 1:0.44 in the described first processing liquid; The volume ratio of the water glass solution and the first treatment liquid is 1:2.2; the first treatment is carried out under a protective atmosphere; the gas of the protective atmosphere includes carbon dioxide gas; the volume of carbon dioxide gas in the protective atmosphere The content is 5.5%; the temperature of the first treatment is 77°C; the time of the first treatment is 88min;
  • the volume ratio of the slurry and the second treatment solution in step (2) is 1:1.33; the second treatment solution includes hydrochloric acid and acetic acid; the molar ratio of hydrochloric acid and acetic acid in the second treatment solution is 1:1.44
  • the second treatment is carried out under an ammonia atmosphere; the content of ammonia in the ammonia atmosphere is 28%; the temperature of the second treatment is 140° C.; the time of the second treatment is 42 minutes.
  • Example 1 The difference from Example 1 is only that the first treatment solution in step (1) is replaced with sulfuric acid of the same concentration and the same amount, and the performance and application effect of the obtained white carbon black for reinforcement are shown in Table 1.
  • Example 1 The difference from Example 1 is only that the second treatment liquid in step (2) is replaced with sulfuric acid of the same concentration and the same amount, and the performance and application effect of the obtained white carbon black for reinforcement are shown in Table 1.
  • Example 1 The difference from Example 1 is only that the protective atmosphere in the first treatment in step (1) does not contain carbon dioxide gas, and the same amount of ammonia gas is used instead, the performance and application effect of the obtained reinforcing silica See Table 1 for details.
  • Example 1 The difference from Example 1 is only that the protective atmosphere in the second treatment in step (1) does not contain ammonia, and is replaced by inert gas argon, and the performance and application effect of the obtained white carbon black for reinforcement are detailed in Table 1.
  • Example 1 The difference from Example 1 is only that the acetic acid in step (2) is replaced with sulfuric acid of the same concentration and the same amount, and the performance and application effect of the obtained white carbon black for reinforcement are shown in Table 1.
  • Example 1 The difference from Example 1 is only that the chloroacetic acid in step (1) is replaced by an equivalent amount of hydrochloric acid, and the properties and application effects of the obtained reinforcing silica are shown in Table 1.
  • the scheme provided by the present application realizes the preparation of high-performance white carbon black through the design of the preparation process and the treatment of specific compositions for multiple times, and the prepared white carbon black
  • the specific surface area can reach 200-230cm 2 /g, and at the same time, the reinforcing performance of silica when used as a reinforcing material is significantly improved, and the mechanical properties of rubber products after reinforcement have been well improved.

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Abstract

A method for preparing white carbon black for reinforcement and the use thereof. The preparation method comprises the following steps: (1) mixing a water glass solution with a first treating liquid, and then subjecting same to first treatment to obtain a slurry, wherein the first treating liquid comprises chloroacetic acid and ammonium citrate; and (2) mixing the slurry obtained in step (1) with a second treating liquid, and then subjecting same to second treatment followed by solid-liquid separation to obtain white carbon black for reinforcement, wherein the second treating liquid comprises hydrochloric acid and acetic acid. By means of the design of the preparation process, the preparation of the high-performance white carbon black is realized by means of secondary treatment by using treating liquids with specific components. The specific surface area of the prepared white carbon black can reach 200-230 cm2/g, and the reinforcing performance of the white carbon black when being used as a reinforcing material is also significantly improved. The mechanical properties of rubber products after reinforcement are improved.

Description

一种补强用白炭黑的制备方法及应用A kind of preparation method and application of white carbon black for reinforcement 技术领域technical field
本申请涉及白炭黑领域，具体涉及一种补强用白炭黑的制备方法及应用。The present application relates to the field of white carbon black, in particular to a preparation method and application of white carbon black for reinforcement.
背景技术Background technique
目前，白炭黑由于具有良好的比表面性能被广泛的应用于各领域中，而白炭黑的制备方法对其性能有明显的影响。At present, silica is widely used in various fields due to its good specific surface properties, and the preparation method of silica has obvious influence on its properties.
如CN107140643A公开了一种高补强易分散白炭黑的制备方法，其以氟硅酸为硅原料、以气氨为氨化剂分步进行氨化反应，并在第二次氨化反应中加入分散剂，制得的白炭黑易分散，具有高补强性能。Disclosed as CN107140643A is a kind of preparation method of high-strength and easily dispersible white carbon black, it uses fluosilicic acid as silicon raw material, is ammoniation agent step by step to carry out ammoniation reaction with gas ammonia, and in the second ammoniation reaction With the addition of dispersant, the prepared white carbon black is easy to disperse and has high reinforcing performance.
CN1337355A公开了一种氟硅酸钠氨化制高补强白炭黑的方法，现工艺方法所得白炭黑比表面积偏低，在橡胶胶料中透明性、补强性差，很难作为高补强白炭黑使用，而且工艺流程长，生产成本高。针对上述问题，提出了Na 2SiF 6分步氨化处理工艺，先一次将总量25-50％的Na 2SiF 6和5-20％氨水在30-45℃下反应，有利于微小胶核的产生，然后再一次或分次加入其余的Na 2SiF 6和氨水在50-70℃下反应，陈化后，经过滤、洗涤、烘干，制得白炭黑。本申请产品比表面积高在130-220m 2/g范围内可调节，DBP吸油值在2.0-3.3范围内可调节。产品可用作制鞋、轮胎的补强材料。 CN1337355A discloses a method for producing high-reinforcing white carbon black by ammoniating sodium fluorosilicate. The specific surface area of white carbon black obtained by the current process method is low, and the transparency and reinforcement in rubber compounds are poor, so it is difficult to be used as high-reinforcing white carbon black. Strong white carbon black is used, and the process is long and the production cost is high. Aiming at the above problems, a Na 2 SiF 6 step-by-step ammoniation treatment process is proposed. Firstly, the total amount of 25-50% Na 2 SiF 6 and 5-20% ammonia water are reacted at 30-45°C, which is beneficial to the tiny glue core. Then add the remaining Na 2 SiF 6 and ammonia water to react at 50-70°C once or in stages, and after aging, filter, wash and dry to obtain white carbon black. The specific surface area of the product of this application can be adjusted within the range of 130-220m 2 /g, and the DBP oil absorption value can be adjusted within the range of 2.0-3.3. The product can be used as a reinforcing material for shoemaking and tires.
然而，目前的补强用白炭黑仍存在补强性能差，比表面积小等问题。However, the current white carbon black for reinforcement still has problems such as poor reinforcement performance and small specific surface area.
发明内容Contents of the invention
本申请提供了一种补强用白炭黑的制备方法及应用，通过对制备过程中工艺的调整，解决了当前工艺制备得到的补强用白炭黑存在的补强性能差，比表面积小的问题。This application provides a preparation method and application of white carbon black for reinforcement. Through the adjustment of the process in the preparation process, the poor reinforcing performance and small specific surface area of the white carbon black for reinforcement prepared by the current process are solved. The problem.
第一方面，本申请提供了一种补强用白炭黑的制备方法，所述制备方法包括如下步骤：In a first aspect, the application provides a method for preparing white carbon black for reinforcement, the preparation method comprising the steps of:
(1)将水玻璃溶液和第一处理液混合后进行第一处理，得到浆液；(1) carry out the first treatment after mixing the water glass solution and the first treatment liquid to obtain a slurry;
(2)将步骤(1)得到的浆液和第二处理液混合后进行第二处理，经固液分离得到所述补强用白炭黑；(2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
其中，所述第一处理液包括氯乙酸和柠檬酸铵；Wherein, the first treatment liquid includes chloroacetic acid and ammonium citrate;
所述第二处理液包括盐酸和乙酸。The second treatment liquid includes hydrochloric acid and acetic acid.
本申请提供的方案，通过对制备过程的设计，采用特定的组成的处理进行多次处理实现了高性能白炭黑的制备，制备得到的白炭黑的比表面积可达200-230cm 2/g，同时显著提升了白炭黑作为补强材料使用时的补强性能，橡胶产品补强后力学性能实现了良好的提升。 The scheme provided by this application realizes the preparation of high-performance white carbon black through the design of the preparation process and multiple treatments with a specific composition, and the specific surface area of the prepared white carbon black can reach 200-230cm 2 /g At the same time, the reinforcing performance of silica when used as a reinforcing material is significantly improved, and the mechanical properties of rubber products after reinforcement have achieved a good improvement.
本申请中，第一处理中采用氯乙酸和柠檬酸铵的组合对水玻璃溶液进行预处理为第二处理提供良好的生成环境，然后在盐酸和乙酸的处理下可直接得到高性能的白炭黑产品，其作为补强材料使用时，补强后的材料力学性能有大幅度的提升。其中，由于柠檬酸胺的引入可以调控白炭黑的沉淀速度进而降低产品中杂质元素的含量，而第二处理中采用盐酸和乙酸的特定组合并在氨气气氛下降低了生成的白炭黑颗粒间的聚集，而保证所得白炭黑具有良好的分散性。In this application, the combination of chloroacetic acid and ammonium citrate is used in the first treatment to pretreat the water glass solution to provide a good environment for the second treatment, and then high-performance white carbon can be directly obtained under the treatment of hydrochloric acid and acetic acid Black product, when used as a reinforcing material, the mechanical properties of the reinforced material are greatly improved. Among them, since the introduction of ammonium citrate can regulate the precipitation rate of silica and then reduce the content of impurity elements in the product, and in the second treatment, a specific combination of hydrochloric acid and acetic acid is used to reduce the amount of silica produced under an ammonia atmosphere. The aggregation between the particles ensures that the obtained silica has good dispersibility.
作为本申请优选的技术方案，步骤(1)所述水玻璃溶液的模数为1.5-2，例如可以是1.5、1.6、1.7、1.8、1.9或2等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。As the preferred technical scheme of the present application, the modulus of the water glass solution described in step (1) is 1.5-2, such as can be 1.5, 1.6, 1.7, 1.8, 1.9 or 2, etc., but not limited to the numerical values listed, the Other unrecited combinations within the scope are also applicable.
作为本申请优选的技术方案，步骤(1)所述第一处理液中氯乙酸和柠檬酸铵的摩尔比为1:(0.3-0.5)，例如可以是1:0.3、1:0.31、1:0.32、1:0.33、1:0.34、1:0.35、1:0.36、1:0.37、1:0.38、1:0.39、1:0.4、1:0.41、1:0.42、1:0.43、1:0.44、1:0.45、1:0.46、1:0.47、1:0.48、1:0.49或1:0.5等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。As the preferred technical scheme of the present application, the mol ratio of chloroacetic acid and ammonium citrate in the first treatment liquid described in step (1) is 1:(0.3-0.5), such as 1:0.3, 1:0.31, 1:0. 0.32, 1:0.33, 1:0.34, 1:0.35, 1:0.36, 1:0.37, 1:0.38, 1:0.39, 1:0.4, 1:0.41, 1:0.42, 1:0.43, 1:0.44, 1:0.45, 1:0.46, 1:0.47, 1:0.48, 1:0.49 or 1:0.5, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
优选地，步骤(1)所述水玻璃溶液和所述第一处理液的体积比为1:(2-3)，例如可以是1:2、1:2.1、1:2.2、1:2.3、1:2.4、1:2.5、1:2.6、1:2.7、1:2.8、1:2.9或1:3等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。Preferably, the volume ratio of the water glass solution and the first treatment liquid in step (1) is 1:(2-3), such as 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9 or 1:3, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
作为本申请优选的技术方案，步骤(1)所述第一处理在保护气氛下进行。As a preferred technical solution of the present application, the first treatment in step (1) is carried out under a protective atmosphere.
优选地，所述保护气氛的气体包括二氧化碳气体。Preferably, the gas in the protective atmosphere includes carbon dioxide gas.
本申请中，第一处理在二氧化碳气体的保护气氛下，可以控制硅元素在溶液中水解的速度，同时配合处理液使液相第一处理结束后达到良好的液相条件，为下第二处理奠定良好的基础，实现了液相中硅的预沉淀。In this application, the first treatment can control the hydrolysis speed of silicon element in the solution under the protective atmosphere of carbon dioxide gas, and at the same time cooperate with the treatment liquid to make the liquid phase reach a good liquid phase condition after the first treatment of the liquid phase, which is the next second treatment. A good foundation is laid and the pre-precipitation of silicon in the liquid phase is realized.
优选地，所述保护气氛中二氧化碳气体的体积含量为2-7％，例如可以是2％、2.2％、2.4％、2.6％、2.8％、3％、3.2％、3.4％、3.6％、3.8％、4％、4.2％、4.4％、 4.6％、4.8％、5％、5.2％、5.4％、5.6％、5.8％、6％、6.2％、6.4％、6.6％、6.8％或7％等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。剩余的气体体积可采用其他惰性组分补足，如氮气，氦气或氩气等。Preferably, the volume content of carbon dioxide gas in the protective atmosphere is 2-7%, such as 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8% %, 4%, 4.2%, 4.4%, 4.6%, 4.8%, 5%, 5.2%, 5.4%, 5.6%, 5.8%, 6%, 6.2%, 6.4%, 6.6%, 6.8% or 7%, etc. , but not limited to the listed values, other unlisted combinations within this range are also applicable. The remaining gas volume can be made up with other inert components, such as nitrogen, helium or argon.
作为本申请优选的技术方案，步骤(1)所述第一处理的温度为70-90℃，例如可以是70℃、71℃、72℃、73℃、74℃、75℃、76℃、77℃、78℃、79℃、80℃、81℃、82℃、83℃、84℃、85℃、86℃、87℃、88℃、89℃或90℃等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。As a preferred technical solution of this application, the temperature of the first treatment in step (1) is 70-90°C, for example, it can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C °C, 78 °C, 79 °C, 80 °C, 81 °C, 82 °C, 83 °C, 84 °C, 85 °C, 86 °C, 87 °C, 88 °C, 89 °C or 90 °C, etc., but not limited to the listed values, Other unrecited combinations within this range are also applicable.
优选地，步骤(1)所述第一处理的时间为70-90min，例如可以是70min、71min、72min、73min、74min、75min、76min、77min、78min、79min、80min、81min、82min、83min、84min、85min、86min、87min、88min、89min或90min等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。Preferably, the first treatment time in step (1) is 70-90min, for example, 70min, 71min, 72min, 73min, 74min, 75min, 76min, 77min, 78min, 79min, 80min, 81min, 82min, 83min, 84min, 85min, 86min, 87min, 88min, 89min or 90min, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
作为本申请优选的技术方案，步骤(2)所述浆液和所述第二处理液的体积比为1:(1.2-1.5)，例如可以是1:1.2、1:1.21、1:1.22、1:1.23、1:1.24、1:1.25、1:1.26、1:1.27、1:1.28、1:1.29、1:1.3、1:1.31、1:1.32、1:1.33、1:1.34、1:1.35、1:1.36、1:1.38、1:1.4、1:1.42、1:1.44、1:1.46、1:1.48或1:1.5等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。As a preferred technical solution of the present application, the volume ratio of the slurry and the second treatment liquid in step (2) is 1:(1.2-1.5), such as 1:1.2, 1:1.21, 1:1.22, 1 :1.23, 1:1.24, 1:1.25, 1:1.26, 1:1.27, 1:1.28, 1:1.29, 1:1.3, 1:1.31, 1:1.32, 1:1.33, 1:1.34, 1:1.35 , 1:1.36, 1:1.38, 1:1.4, 1:1.42, 1:1.44, 1:1.46, 1:1.48 or 1:1.5, etc., but not limited to the listed values, other unlisted combinations The same applies.
优选地，步骤(2)所述第二处理液中盐酸和乙酸的摩尔比为1:(1.2-1.5)，例如可以是1:1.2、1:1.21、1:1.22、1:1.23、1:1.24、1:1.25、1:1.26、1:1.27、1:1.28、1:1.29、1:1.3、1:1.31、1:1.32、1:1.33、1:1.34、1:1.35、1:1.36、1:1.38、1:1.4、1:1.42、1:1.44、1:1.46、1:1.48或1:1.5等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。Preferably, the molar ratio of hydrochloric acid and acetic acid in the second treatment liquid described in step (2) is 1:(1.2-1.5), such as can be 1:1.2, 1:1.21, 1:1.22, 1:1.23, 1: 1.24, 1:1.25, 1:1.26, 1:1.27, 1:1.28, 1:1.29, 1:1.3, 1:1.31, 1:1.32, 1:1.33, 1:1.34, 1:1.35, 1:1.36, 1:1.38, 1:1.4, 1:1.42, 1:1.44, 1:1.46, 1:1.48 or 1:1.5, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
作为本申请优选的技术方案，步骤(2)所述第二处理在氨气氛围下进行。As a preferred technical solution of the present application, the second treatment in step (2) is carried out under an ammonia atmosphere.
优选地，所述氨气氛围中氨气的含量为25-30％，例如可以是25％、25.2％、25.4％、25.6％、25.8％、26％、26.2％、26.4％、26.8％、27％、27.2％、27.4％、27.6％、27.8％、28％、28.2％、28.4％、28.6％、28.8％、29％、29.2％、29.4％、29.6％、29.8％或30％等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。剩余的气体体积可采用其他惰性组分补足，如氮气，氦气或氩气等。Preferably, the content of ammonia in the ammonia atmosphere is 25-30%, such as 25%, 25.2%, 25.4%, 25.6%, 25.8%, 26%, 26.2%, 26.4%, 26.8%, 27% %, 27.2%, 27.4%, 27.6%, 27.8%, 28%, 28.2%, 28.4%, 28.6%, 28.8%, 29%, 29.2%, 29.4%, 29.6%, 29.8% or 30%, etc., but not Limited to the listed values, other unlisted combinations within this range are also applicable. The remaining gas volume can be made up with other inert components, such as nitrogen, helium or argon.
本申请中，在第二处理中引入氨气氛围在第一处理的基础上，保证了第二处理中形成的白炭黑具有良好的结构，避免了白炭黑的聚集，确保了制备得到 的白炭黑具有良好的分散性能和比表面积。In this application, on the basis of the first treatment, the introduction of ammonia gas atmosphere in the second treatment ensures that the silica formed in the second treatment has a good structure, avoids the aggregation of silica, and ensures that the prepared Silica has good dispersion performance and specific surface area.
作为本申请优选的技术方案，步骤(2)所述第二处理的温度为120-150℃，例如可以是120℃、122℃、124℃、126℃、128℃、130℃、132℃、134℃、136℃、138℃、140℃、142℃、144℃、146℃、148℃或150℃等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。As a preferred technical solution of this application, the temperature of the second treatment in step (2) is 120-150°C, for example, it can be 120°C, 122°C, 124°C, 126°C, 128°C, 130°C, 132°C, 134°C °C, 136 °C, 138 °C, 140 °C, 142 °C, 144 °C, 146 °C, 148 °C or 150 °C, etc., but not limited to the listed values, and other unlisted combinations within this range are also applicable.
优选地，步骤(2)所述第二处理的时间为30-45min，例如可以是30min、31min、32min、33min、34min、35min、36min、37min、38min、39min、40min、41min、42min、43min、44min或45min等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。Preferably, the time for the second treatment in step (2) is 30-45min, such as 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min, 40min, 41min, 42min, 43min, 44min or 45min, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
作为本申请优选的技术方案，所述制备方法包括如下步骤：As a preferred technical solution of the present application, the preparation method includes the following steps:
(1)将水玻璃溶液和第一处理液混合后进行第一处理，得到浆液；(1) carry out the first treatment after mixing the water glass solution and the first treatment liquid to obtain a slurry;
(2)将步骤(1)得到的浆液和第二处理液混合后进行第二处理，经固液分离得到所述补强用白炭黑；(2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
其中，步骤(1)所述水玻璃溶液的模数为1.5-2；所述第一处理液包括氯乙酸和柠檬酸铵；所述第一处理液中氯乙酸和柠檬酸铵的摩尔比为1:(0.3-0.5)；所述水玻璃溶液和所述第一处理液的体积比为1:(2-3)；所述第一处理在保护气氛下进行；所述保护气氛的气体包括二氧化碳气体；所述保护气氛中二氧化碳气体的体积含量为2-7％；所述第一处理的温度为70-90℃；所述第一处理的时间为70-90min；Wherein, the modulus of the water glass solution described in step (1) is 1.5-2; the first treatment solution includes chloroacetic acid and ammonium citrate; the mol ratio of chloroacetic acid and ammonium citrate in the first treatment solution is 1:(0.3-0.5); the volume ratio of the water glass solution and the first treatment liquid is 1:(2-3); the first treatment is carried out under a protective atmosphere; the gas of the protective atmosphere includes Carbon dioxide gas; the volume content of carbon dioxide gas in the protective atmosphere is 2-7%; the temperature of the first treatment is 70-90°C; the time of the first treatment is 70-90min;
步骤(2)所述浆液和所述第二处理液的体积比为1:(1.2-1.5)；所述第二处理液包括盐酸和乙酸；所述第二处理液中盐酸和乙酸的摩尔比为1:(1.2-1.5)；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的含量为25-30％；所述第二处理的温度为120-150℃；所述第二处理的时间为30-45min。The volume ratio of the slurry and the second treatment solution in step (2) is 1:(1.2-1.5); the second treatment solution includes hydrochloric acid and acetic acid; the mol ratio of hydrochloric acid and acetic acid in the second treatment solution It is 1: (1.2-1.5); the second treatment is carried out under an ammonia atmosphere; the content of ammonia in the ammonia atmosphere is 25-30%; the temperature of the second treatment is 120-150°C; The time of the second treatment is 30-45min.
第二方面，本申请提供了如第一方面所述制备方法得倒补强用白炭黑的应用，所述补强用白炭黑用于橡胶产品补强。In the second aspect, the present application provides the application of the white carbon black for reinforcement obtained by the preparation method described in the first aspect, and the white carbon black for reinforcement is used for reinforcing rubber products.
与现有技术方案相比，本申请至少具有以下有益效果：Compared with the prior art solutions, the present application has at least the following beneficial effects:
(1)本申请提供的方案，通过对制备过程的设计，采用特定的组成的处理进行多次处理实现了高性能白炭黑的制备，制备得到的白炭黑的比表面积可达200-230cm 2/g，同时显著提升了白炭黑作为补强材料使用时的补强性能，橡胶产品补强后力学性能实现了良好的提升。 (1) The scheme provided by this application realizes the preparation of high-performance white carbon black through the design of the preparation process and multiple treatments with specific compositions, and the specific surface area of the prepared white carbon black can reach 200-230cm 2 /g, and at the same time, the reinforcing performance of silica when used as a reinforcing material is significantly improved, and the mechanical properties of rubber products after reinforcement have achieved a good improvement.
(2)本申请中，通过在多次处理过程中引入特定的气氛辅助，进一步强化了所得白炭黑的补强性能。应用于橡胶产品进行补强后，硬度JIS可达到90以上，拉伸强度可达18.2MPa以上，延伸率可达660.5％以上。(2) In this application, the reinforcement performance of the obtained silica is further enhanced by introducing specific atmosphere assistance in the multiple treatment processes. After being applied to rubber products for reinforcement, the hardness JIS can reach more than 90, the tensile strength can reach more than 18.2MPa, and the elongation can reach more than 660.5%.
具体实施方式Detailed ways
为更好地说明本申请，便于理解本申请的技术方案，本申请的典型但非限制性的实施例如下：In order to better describe the present application and facilitate the understanding of the technical scheme of the present application, the typical but non-limiting examples of the present application are as follows:
实施例1Example 1
本实施例提供一种补强用白炭黑的制备方法，所述制备方法包括如下步骤：This embodiment provides a preparation method of white carbon black for reinforcement, the preparation method comprising the following steps:
(1)将水玻璃溶液和第一处理液混合后进行第一处理，得到浆液；(1) carry out the first treatment after mixing the water glass solution and the first treatment liquid to obtain a slurry;
(2)将步骤(1)得到的浆液和第二处理液混合后进行第二处理，经固液分离得到所述补强用白炭黑；(2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
步骤(1)所述水玻璃溶液的模数为1.7；所述第一处理液包括氯乙酸和柠檬酸铵；所述第一处理液中氯乙酸和柠檬酸铵的摩尔比为1:0.4；所述水玻璃溶液和所述第一处理液的体积比为1:2.5；所述第一处理在保护气氛下进行；所述保护气氛的气体包括二氧化碳气体；所述保护气氛中二氧化碳气体的体积含量为4％；所述第一处理的温度为80℃；所述第一处理的时间为80min；The modulus of the described water glass solution of step (1) is 1.7; Described the first processing liquid comprises chloroacetic acid and ammonium citrate; The mol ratio of chloroacetic acid and ammonium citrate is 1:0.4 in the described first processing liquid; The volume ratio of the water glass solution and the first treatment liquid is 1:2.5; the first treatment is carried out under a protective atmosphere; the gas of the protective atmosphere includes carbon dioxide gas; the volume of carbon dioxide gas in the protective atmosphere The content is 4%; the temperature of the first treatment is 80°C; the time of the first treatment is 80min;
步骤(2)所述浆液和所述第二处理液的体积比为1:1.35；所述第二处理液包括盐酸和乙酸；所述第二处理液中盐酸和乙酸的摩尔比为1:1.35；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的含量为27％；所述第二处理的温度为130℃；所述第二处理的时间为37min。The volume ratio of the slurry and the second treatment solution in step (2) is 1:1.35; the second treatment solution includes hydrochloric acid and acetic acid; the molar ratio of hydrochloric acid and acetic acid in the second treatment solution is 1:1.35 The second treatment is carried out under an ammonia atmosphere; the content of ammonia in the ammonia atmosphere is 27%; the temperature of the second treatment is 130° C.; the time of the second treatment is 37 minutes.
所得补强用白炭黑的性能及其应用效果详见表1。The properties and application effects of the obtained reinforcing silica are shown in Table 1.
实施例2Example 2
本实施例提供一种补强用白炭黑的制备方法，所述制备方法包括如下步骤：This embodiment provides a preparation method of white carbon black for reinforcement, the preparation method comprising the following steps:
(1)将水玻璃溶液和第一处理液混合后进行第一处理，得到浆液；(1) carry out the first treatment after mixing the water glass solution and the first treatment liquid to obtain a slurry;
(2)将步骤(1)得到的浆液和第二处理液混合后进行第二处理，经固液分离得到所述补强用白炭黑；(2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
步骤(1)所述水玻璃溶液的模数为2；所述第一处理液包括氯乙酸和柠檬酸铵；所述第一处理液中氯乙酸和柠檬酸铵的摩尔比为1:0.5；所述水玻璃溶液和所述第一处理液的体积比为1:2；所述第一处理在保护气氛下进行；所述保护 气氛的气体包括二氧化碳气体；所述保护气氛中二氧化碳气体的体积含量为2％；所述第一处理的温度为70℃；所述第一处理的时间为90min；The modulus of the described water glass solution of step (1) is 2; Described the first processing liquid comprises chloroacetic acid and ammonium citrate; The mol ratio of chloroacetic acid and ammonium citrate is 1:0.5 in the described first processing liquid; The volume ratio of the water glass solution and the first treatment liquid is 1:2; the first treatment is carried out under a protective atmosphere; the gas of the protective atmosphere includes carbon dioxide gas; the volume of carbon dioxide gas in the protective atmosphere The content is 2%; the temperature of the first treatment is 70°C; the time of the first treatment is 90min;
步骤(2)所述浆液和所述第二处理液的体积比为1:1.5；所述第二处理液包括盐酸和乙酸；所述第二处理液中盐酸和乙酸的摩尔比为1:1.2；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的含量为25％；所述第二处理的温度为150℃；所述第二处理的时间为45min。The volume ratio of the slurry and the second treatment solution in step (2) is 1:1.5; the second treatment solution includes hydrochloric acid and acetic acid; the molar ratio of hydrochloric acid and acetic acid in the second treatment solution is 1:1.2 ; The second treatment is carried out under an ammonia atmosphere; the content of ammonia in the ammonia atmosphere is 25%; the temperature of the second treatment is 150° C.; the time of the second treatment is 45 minutes.
所得补强用白炭黑的性能及其应用效果详见表1。The properties and application effects of the obtained reinforcing silica are shown in Table 1.
实施例3Example 3
本实施例提供一种补强用白炭黑的制备方法，所述制备方法包括如下步骤：This embodiment provides a preparation method of white carbon black for reinforcement, the preparation method comprising the following steps:
(1)将水玻璃溶液和第一处理液混合后进行第一处理，得到浆液；(1) carry out the first treatment after mixing the water glass solution and the first treatment liquid to obtain a slurry;
(2)将步骤(1)得到的浆液和第二处理液混合后进行第二处理，经固液分离得到所述补强用白炭黑；(2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
步骤(1)所述水玻璃溶液的模数为1.5；所述第一处理液包括氯乙酸和柠檬酸铵；所述第一处理液中氯乙酸和柠檬酸铵的摩尔比为1:0.5；所述水玻璃溶液和所述第一处理液的体积比为1:3；所述第一处理在保护气氛下进行；所述保护气氛的气体包括二氧化碳气体；所述保护气氛中二氧化碳气体的体积含量为7％；所述第一处理的温度为90℃；所述第一处理的时间为70min；The modulus of the described water glass solution of step (1) is 1.5; Described the first processing liquid comprises chloroacetic acid and ammonium citrate; The mol ratio of chloroacetic acid and ammonium citrate is 1:0.5 in the described first processing liquid; The volume ratio of the water glass solution and the first treatment liquid is 1:3; the first treatment is carried out under a protective atmosphere; the gas of the protective atmosphere includes carbon dioxide gas; the volume of carbon dioxide gas in the protective atmosphere The content is 7%; the temperature of the first treatment is 90°C; the time of the first treatment is 70min;
步骤(2)所述浆液和所述第二处理液的体积比为1:1.2；所述第二处理液包括盐酸和乙酸；所述第二处理液中盐酸和乙酸的摩尔比为1:1.5；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的含量为30％；所述第二处理的温度为120℃；所述第二处理的时间为30min。The volume ratio of the slurry and the second treatment solution in step (2) is 1:1.2; the second treatment solution includes hydrochloric acid and acetic acid; the molar ratio of hydrochloric acid and acetic acid in the second treatment solution is 1:1.5 ; The second treatment is carried out under an ammonia atmosphere; the content of ammonia in the ammonia atmosphere is 30%; the temperature of the second treatment is 120° C.; the time of the second treatment is 30 minutes.
所得补强用白炭黑的性能及其应用效果详见表1。The properties and application effects of the obtained reinforcing silica are shown in Table 1.
实施例4Example 4
本实施例提供一种补强用白炭黑的制备方法，所述制备方法包括如下步骤：This embodiment provides a preparation method of white carbon black for reinforcement, the preparation method comprising the following steps:
(1)将水玻璃溶液和第一处理液混合后进行第一处理，得到浆液；(1) carry out the first treatment after mixing the water glass solution and the first treatment liquid to obtain a slurry;
(2)将步骤(1)得到的浆液和第二处理液混合后进行第二处理，经固液分离得到所述补强用白炭黑；(2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
步骤(1)所述水玻璃溶液的模数为1.85；所述第一处理液包括氯乙酸和柠檬酸铵；所述第一处理液中氯乙酸和柠檬酸铵的摩尔比为1:0.44；所述水玻璃溶液和所述第一处理液的体积比为1:2.2；所述第一处理在保护气氛下进行；所述 保护气氛的气体包括二氧化碳气体；所述保护气氛中二氧化碳气体的体积含量为5.5％；所述第一处理的温度为77℃；所述第一处理的时间为88min；The modulus of the described water glass solution of step (1) is 1.85; Described the first processing liquid comprises chloroacetic acid and ammonium citrate; The mol ratio of chloroacetic acid and ammonium citrate is 1:0.44 in the described first processing liquid; The volume ratio of the water glass solution and the first treatment liquid is 1:2.2; the first treatment is carried out under a protective atmosphere; the gas of the protective atmosphere includes carbon dioxide gas; the volume of carbon dioxide gas in the protective atmosphere The content is 5.5%; the temperature of the first treatment is 77°C; the time of the first treatment is 88min;
步骤(2)所述浆液和所述第二处理液的体积比为1:1.33；所述第二处理液包括盐酸和乙酸；所述第二处理液中盐酸和乙酸的摩尔比为1:1.44；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的含量为28％；所述第二处理的温度为140℃；所述第二处理的时间为42min。The volume ratio of the slurry and the second treatment solution in step (2) is 1:1.33; the second treatment solution includes hydrochloric acid and acetic acid; the molar ratio of hydrochloric acid and acetic acid in the second treatment solution is 1:1.44 The second treatment is carried out under an ammonia atmosphere; the content of ammonia in the ammonia atmosphere is 28%; the temperature of the second treatment is 140° C.; the time of the second treatment is 42 minutes.
所得补强用白炭黑的性能及其应用效果详见表1。The properties and application effects of the obtained reinforcing silica are shown in Table 1.
对比例1Comparative example 1
与实施例1的区别仅在于将步骤(1)中的第一处理液替换为等量等浓度的硫酸，所得补强用白炭黑的性能及其应用效果详见表1。The difference from Example 1 is only that the first treatment solution in step (1) is replaced with sulfuric acid of the same concentration and the same amount, and the performance and application effect of the obtained white carbon black for reinforcement are shown in Table 1.
对比例2Comparative example 2
与实施例1的区别仅在于将步骤(2)中的第二处理液替换为等量等浓度的硫酸，所得补强用白炭黑的性能及其应用效果详见表1。The difference from Example 1 is only that the second treatment liquid in step (2) is replaced with sulfuric acid of the same concentration and the same amount, and the performance and application effect of the obtained white carbon black for reinforcement are shown in Table 1.
对比例3Comparative example 3
与实施例1的区别仅在于将步骤(1)中的第一处理中的保护气氛中不含有二氧化碳气体，采用等量的氨气的替代，所得补强用白炭黑的性能及其应用效果详见表1。The difference from Example 1 is only that the protective atmosphere in the first treatment in step (1) does not contain carbon dioxide gas, and the same amount of ammonia gas is used instead, the performance and application effect of the obtained reinforcing silica See Table 1 for details.
对比例3Comparative example 3
与实施例1的区别仅在于将步骤(1)中的第二处理中的保护气氛中不含有氨气，采用惰性气体氩气替代，所得补强用白炭黑的性能及其应用效果详见表1。The difference from Example 1 is only that the protective atmosphere in the second treatment in step (1) does not contain ammonia, and is replaced by inert gas argon, and the performance and application effect of the obtained white carbon black for reinforcement are detailed in Table 1.
对比例4Comparative example 4
与实施例1的区别仅在于将步骤(2)中的乙酸换为等量等浓度的硫酸，所得补强用白炭黑的性能及其应用效果详见表1。The difference from Example 1 is only that the acetic acid in step (2) is replaced with sulfuric acid of the same concentration and the same amount, and the performance and application effect of the obtained white carbon black for reinforcement are shown in Table 1.
对比例5Comparative example 5
与实施例1的区别仅在于将步骤(1)中的氯乙酸替换为等量的盐酸，所得补强用白炭黑的性能及其应用效果详见表1。The difference from Example 1 is only that the chloroacetic acid in step (1) is replaced by an equivalent amount of hydrochloric acid, and the properties and application effects of the obtained reinforcing silica are shown in Table 1.
表1Table 1
Figure PCTCN2021116856-appb-000001
Figure PCTCN2021116856-appb-000001
Figure PCTCN2021116856-appb-000002
Figure PCTCN2021116856-appb-000002
通过上述实施例和对比例的结果可知，本申请提供的方案，通过对制备过程的设计，采用特定的组成的处理进行多次处理实现了高性能白炭黑的制备，制备得到的白炭黑的比表面积可达200-230cm 2/g，同时显著提升了白炭黑作为补强材料使用时的补强性能，橡胶产品补强后力学性能实现了良好的提升。 From the results of the above-mentioned examples and comparative examples, it can be known that the scheme provided by the present application realizes the preparation of high-performance white carbon black through the design of the preparation process and the treatment of specific compositions for multiple times, and the prepared white carbon black The specific surface area can reach 200-230cm 2 /g, and at the same time, the reinforcing performance of silica when used as a reinforcing material is significantly improved, and the mechanical properties of rubber products after reinforcement have been well improved.
申请人声明，本申请通过上述实施例来说明本申请的详细结构特征，但本申请并不局限于上述详细结构特征，即不意味着本申请必须依赖上述详细结构特征才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请所选用部件的等效替换以及辅助部件的增加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。The applicant declares that the present application illustrates the detailed structural features of the present application through the above embodiments, but the present application is not limited to the above detailed structural features, that is, it does not mean that the application must rely on the above detailed structural features to be implemented. Those skilled in the art should understand that any improvement to the application, equivalent replacement of the components selected in the application, addition of auxiliary components, selection of specific methods, etc., all fall within the scope of protection and disclosure of the application.
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。The preferred embodiments of the present application have been described in detail above, but the present application is not limited to the specific details in the above-mentioned embodiments. Within the scope of the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application. These simple modifications All belong to the scope of protection of this application.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。In addition, any combination of various implementations of the present application can also be made, as long as they do not violate the idea of the present application, they should also be regarded as the content disclosed in the present application.

Claims (11)

  1. 一种补强用白炭黑的制备方法，其包括如下步骤：A preparation method of white carbon black for reinforcement, comprising the steps of:
    (1)将水玻璃溶液和第一处理液混合后进行第一处理，得到浆液；(1) carry out the first treatment after mixing the water glass solution and the first treatment liquid to obtain a slurry;
    (2)将步骤(1)得到的浆液和第二处理液混合后进行第二处理，经固液分离得到所述补强用白炭黑；(2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
    其中，所述第一处理液包括氯乙酸和柠檬酸铵；Wherein, the first treatment liquid includes chloroacetic acid and ammonium citrate;
    所述第二处理液包括盐酸和乙酸。The second treatment liquid includes hydrochloric acid and acetic acid.
  2. 如权利要求1所述的制备方法，其中，步骤(1)所述水玻璃溶液的模数为1.5-2。preparation method as claimed in claim 1, wherein, the modulus of the described water glass solution of step (1) is 1.5-2.
  3. 如权利要求1或2所述的制备方法，其中，步骤(1)所述第一处理液中氯乙酸和柠檬酸铵的摩尔比为1:(0.3-0.5)。The preparation method according to claim 1 or 2, wherein the mol ratio of chloroacetic acid and ammonium citrate in the first treatment liquid described in step (1) is 1:(0.3-0.5).
  4. 如权利要求1-3任一项所述的制备方法，其中，步骤(1)所述水玻璃溶液和所述第一处理液的体积比为1:(2-3)。The preparation method according to any one of claims 1-3, wherein the water glass solution of step (1) and the volume ratio of the first treatment liquid are 1:(2-3).
  5. 如权利要求1-4任一项所述的制备方法，其中，步骤(1)所述第一处理在保护气氛下进行；The preparation method according to any one of claims 1-4, wherein the first treatment in step (1) is carried out under a protective atmosphere;
    任选地，所述保护气氛的气体包括二氧化碳气体；Optionally, the gas of the protective atmosphere includes carbon dioxide gas;
    任选地，所述保护气氛中二氧化碳气体的体积含量为2-7％。Optionally, the volume content of carbon dioxide gas in the protective atmosphere is 2-7%.
  6. 如权利要求1-5任一项所述的制备方法，其中，步骤(1)所述第一处理的温度为70-90℃；The preparation method according to any one of claims 1-5, wherein the temperature of the first treatment in step (1) is 70-90°C;
    任选地，步骤(1)所述第一处理的时间为70-90min。Optionally, the time for the first treatment in step (1) is 70-90 minutes.
  7. 如权利要求1-6任一项所述的制备方法，其中，步骤(2)所述浆液和所述第二处理液的体积比为1:(1.2-1.5)；The preparation method according to any one of claims 1-6, wherein the volume ratio of the slurry in step (2) and the second treatment liquid is 1:(1.2-1.5);
    任选地，步骤(2)所述第二处理液中盐酸和乙酸的摩尔比为1:(1.2-1.5)。Optionally, the molar ratio of hydrochloric acid and acetic acid in the second treatment liquid in step (2) is 1:(1.2-1.5).
  8. 如权利要求1-7任一项所述的制备方法，其中，步骤(2)所述第二处理在氨气氛围下进行；The preparation method according to any one of claims 1-7, wherein the second treatment in step (2) is carried out under an ammonia atmosphere;
    任选地，所述氨气氛围中氨气的含量为25-30％。Optionally, the content of ammonia in the ammonia atmosphere is 25-30%.
  9. 如权利要求1-8任一项所述的制备方法，其中，步骤(2)所述第二处理的温度为120-150℃；The preparation method according to any one of claims 1-8, wherein the temperature of the second treatment in step (2) is 120-150°C;
    任选地，步骤(2)所述第二处理的时间为30-45min。Optionally, the time for the second treatment in step (2) is 30-45min.
  10. 如权利要求1-9任一项所述的制备方法，其中，所述制备方法包括如下步骤：The preparation method according to any one of claims 1-9, wherein the preparation method comprises the steps of:
    (1)将水玻璃溶液和第一处理液混合后进行第一处理，得到浆液；(1) carry out the first treatment after mixing the water glass solution and the first treatment liquid to obtain a slurry;
    (2)将步骤(1)得到的浆液和第二处理液混合后进行第二处理，经固液分离得到所述补强用白炭黑；(2) performing the second treatment after mixing the slurry obtained in step (1) with the second treatment liquid, and obtaining the white carbon black for reinforcement through solid-liquid separation;
    其中，步骤(1)所述水玻璃溶液的模数为1.5-2；所述第一处理液包括氯乙酸和柠檬酸铵；所述第一处理液中氯乙酸和柠檬酸铵的摩尔比为1:(0.3-0.5)；所述水玻璃溶液和所述第一处理液的体积比为1:(2-3)；所述第一处理在保护气氛下进行；所述保护气氛的气体包括二氧化碳气体；所述保护气氛中二氧化碳气体的体积含量为2-7％；所述第一处理的温度为70-90℃；所述第一处理的时间为70-90min；Wherein, the modulus of the water glass solution described in step (1) is 1.5-2; the first treatment solution includes chloroacetic acid and ammonium citrate; the mol ratio of chloroacetic acid and ammonium citrate in the first treatment solution is 1:(0.3-0.5); the volume ratio of the water glass solution and the first treatment liquid is 1:(2-3); the first treatment is carried out under a protective atmosphere; the gas of the protective atmosphere includes Carbon dioxide gas; the volume content of carbon dioxide gas in the protective atmosphere is 2-7%; the temperature of the first treatment is 70-90°C; the time of the first treatment is 70-90min;
    步骤(2)所述浆液和所述第二处理液的体积比为1:(1.2-1.5)；所述第二处理液包括盐酸和乙酸；所述第二处理液中盐酸和乙酸的摩尔比为1:(1.2-1.5)；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的含量为25-30％；所述第二处理的温度为120-150℃；所述第二处理的时间为30-45min。The volume ratio of the slurry and the second treatment solution in step (2) is 1:(1.2-1.5); the second treatment solution includes hydrochloric acid and acetic acid; the mol ratio of hydrochloric acid and acetic acid in the second treatment solution It is 1: (1.2-1.5); the second treatment is carried out under an ammonia atmosphere; the content of ammonia in the ammonia atmosphere is 25-30%; the temperature of the second treatment is 120-150°C; The time of the second treatment is 30-45min.
  11. 如权利要求1-10任一项所述制备方法得到的补强用白炭黑的应用，其包括将所述补强用白炭黑用于橡胶产品的补强。The application of the white carbon black for reinforcement obtained by the preparation method according to any one of claims 1-10 comprises using the white carbon black for reinforcement for the reinforcement of rubber products.
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