CN109678529B - Binding agent for producing three major parts of steel-making continuous casting and magnesia carbon brick - Google Patents
Binding agent for producing three major parts of steel-making continuous casting and magnesia carbon brick Download PDFInfo
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- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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Abstract
The invention discloses a bonding agent for producing three major steel-making and continuous casting pieces and magnesia carbon bricks, which is prepared from basic components and a cross-linking agent; the base component comprises the following raw materials in percentage by weight: 60-75% of fructose syrup, 7-10% of saccharified starch, 2.5-4% of xylitol and 15-26% of ethylene glycol; the cross-linking agent is 1 per mill of the weight of the basic component. The binder of the present invention has little decomposition gas discharged and no unpleasant odor; the refractory material produced by the method has good chilling and shock resistance; and the mixing performance and the forming performance are equal to or better than those of the phenolic resin.
Description
Technical Field
The invention relates to the technical field of production of binders for aluminum-carbon and magnesia-carbon refractory materials, in particular to a binder for production of three major parts of steel-making and continuous casting and magnesia-carbon bricks.
Background
The three major parts of the steel-making continuous casting comprise a long nozzle for continuous casting, an integral stopper rod and an immersion nozzle, are very important functional refractory materials in the continuous casting process, and have the functions of connecting a steel ladle, a tundish and a crystallizer into a whole, controlling flow and guiding molten steel, preventing secondary oxidation of the molten steel and realizing the continuous casting process.
The magnesia carbon brick is a smelting refractory material, fully exerts the advantages of ultrahigh melting point, high temperature and strength and low thermal expansion rate of graphite carbon, has the advantages of high refractoriness, good slag erosion resistance, small thermal shock resistance and high-temperature creep deformation and the like, and is widely applied to continuous casting systems of steelmaking blast furnaces, electric furnaces and refining furnaces.
At present, phenolic resin or furfural resin and ethanol are used as binding agents in the production of three major steel-making and continuous casting pieces and magnesia carbon bricks, and in addition, no other substances are reported to be successful as the binding agents. Phenolic resins exhibit good performance when blended with carbonaceous refractory materials such as graphite and have a large amount of residual carbon when fired, but the use of phenolic resins has the following disadvantages and problems:
1. the phenolic resin is formed by the catalytic reaction of formaldehyde and phenol, but even if the reaction is completed, the phenolic resin has free phenol and formaldehyde, and the phenolic resin is harmful to human bodies when heated. Furthermore, when the phenolic resin is carbonized at a temperature ranging from normal temperature to 650 ℃, decomposition gases such as water vapor, chlorine, ethylene, phenol, cresol, xylene and the like are discharged, and among these components, phenol, cresol and xylene generate odor, and for example, after an unburned carbon-containing product is dried at about 200 ℃, the product can be supplied to the market as a lining material of a kiln, and when the lining material is used for building a plug furnace, the lining material needs to be preheated to about 1000 ℃ in actual use, and when the lining material is preheated, the phenolic resin is decomposed to generate gas, and the gas is discharged from the furnace plug, so that air pollution and odor are caused, and the gas is harmful to human bodies.
2. In the case of using a phenol resin as a binder, since the phenol resin has good press moldability, the final product has a dense structure and a small amount of open pores, and therefore, the structure is easily broken by the release of decomposition gas during heating, that is, the product after curing by drying has a structure with few open pores and almost no air permeability. While helping to improve the strength of the dried article, such structures can prevent the phenolic resin from decomposing gases above the drying and hardening temperatures from being generated and escaping, causing an increase in internal pressure, resulting in structural cracking or breakage.
3. Since the carbon produced from the phenolic resin is glassy carbon having poor resistance to shock and heat shock, that is, amorphous carbon, the resultant product has poor resistance to shock and heat shock, although a large amount of residual carbon is produced during firing.
When carbon-containing products with shock resistance are required to be produced, phenolic resin is generally not selected, and asphalt is used as a binding agent. Although the pitch-bonded carbonaceous product has good resistance to shock heating, it is disadvantageous in that the pitch is solid at ordinary temperature, must be kneaded by heating to a temperature higher than the softening point, and further, the kneading and molding properties of the pitch are lower than those of the phenolic resin.
As a method for producing a carbonaceous product using neither a phenol resin nor pitch (JP Hei 7-504741), according to this technique, an organic high molecular compound such as a polyacrylate in the form of an aqueous solution or a suspension is inferior in properties to a phenol resin, the volume weight of the resulting compact is low, and the kneading properties and pressing properties of this binder are also inferior to those of a phenol resin.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a bonding agent for producing three major steel-making and continuous casting pieces and magnesia carbon bricks. The binder has little decomposition gas discharged and no unpleasant odor; the refractory material produced by the method has good chilling and shock resistance; and the mixing performance and the forming performance are equal to or better than those of the phenolic resin.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, a bonding agent is provided, which is made from a base component and a cross-linking agent;
the base component comprises the following raw materials in percentage by weight:
60-75% of fructose syrup, 7-10% of saccharified starch, 2.5-4% of xylitol and 15-26% of ethylene glycol;
the cross-linking agent is 1 per mill of the weight of the basic component.
Preferably, the base component consists of the following raw materials in percentage by weight:
69% of fructose syrup, 7.5% of saccharified starch, 3.5% of xylitol and 20% of ethylene glycol.
Preferably, the cross-linking agent is Benzoyl Peroxide (BPO).
In a second aspect of the present invention, there is provided a method for preparing the above binder, comprising the steps of:
mixing fructose syrup, saccharified starch, xylitol and ethylene glycol in proportion to serve as basic components; and adding a cross-linking agent into the basic component, and uniformly mixing to obtain the bonding agent.
In a third aspect of the invention, the application of the bonding agent in the production of three major steel-making continuous casting pieces is provided.
In a fourth aspect of the invention, the use of the above binder in the production of magnesia carbon bricks is provided.
In the fifth aspect of the invention, the steelmaking continuous casting three large parts are provided, and raw materials for preparing the steelmaking continuous casting three large parts comprise 6-10% (weight percentage) of the bonding agent.
The invention also provides a preparation method of the three steel-making continuous casting parts, which comprises the following steps:
mixing the raw materials for preparing the three main parts of the steelmaking continuous casting, and performing compression molding to obtain a semi-finished product; and then carrying out heat treatment on the semi-finished product to obtain three steel-making continuous casting pieces.
In a sixth aspect of the present invention, there is provided a magnesia carbon brick, wherein the raw materials for preparing the magnesia carbon brick comprise 2-4% (by weight) of the above-mentioned binder.
The invention also provides a preparation method of the magnesia carbon brick, which comprises the following steps:
the raw materials for preparing the magnesia carbon brick are mixed and pressed into a green brick, and then the green brick is heated to prepare the magnesia carbon brick.
The invention has the beneficial effects that:
the invention provides a brand-new bonding agent for producing three major steel-making and continuous casting pieces and magnesia carbon bricks, which takes fructose syrup as a solvent, is added with saccharified starch, xylitol and glycol simultaneously to form a basic component of the bonding agent, and then adds a certain amount of cross-linking agent into the basic component, so that the prepared basic component can not generate precipitation and can be better suspended. The invention improves the mixing property and the formability of the binding agent and the chilling and shock heat resistance of the refractory material produced by the binding agent by utilizing the matching effect of the raw material components with specific contents; in addition, the binding agent of the invention does not contain phenolic resin and furfural resin, and almost no decomposition gas is discharged, so no unpleasant odor is generated.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As introduced in the background art, the binding agent adopted by the prior three major parts of steel-making and continuous casting and the production of magnesia carbon bricks mainly takes phenolic resin or furfural resin as an effective component, but the phenolic resin or furfural resin can discharge decomposed gas during carbonization to form unpleasant odor, cause air pollution and harm to human bodies; the formed product has few open pores, and the product structure is cracked or broken due to the release of decomposition gas during heating; in addition, the final product formed by using phenolic resin as a binder has poor shock resistance. If other raw materials are used for replacing phenolic resin or furfural resin, such as asphalt and acrylate, although some defects of the phenolic resin as a binding agent can be improved, the mixing performance and the pressing performance of the prepared binding agent are lower than those of the binding agent prepared from the phenolic resin. Therefore, the existing bonding agent for producing three major steel-making and continuous casting and magnesia carbon bricks still has a plurality of defects.
Based on the above, the invention aims to provide a novel binding agent for three major steel-making and continuous casting and magnesia carbon brick production, which can solve the problems of the phenolic resin or furfural resin binding agent that decomposed gas is discharged, the produced refractory material has poor chilling and heat resistance, the product structure is easy to crack or break, and the like; the mixing performance and the forming performance of the bonding agent provided by the invention are equal to or superior to those of phenolic resin.
In one embodiment of the invention, the concrete raw material composition of the bonding agent for producing three major steel-making and continuous casting pieces and magnesia carbon bricks is given as follows: is prepared from basic components and cross-linking agent;
the base component comprises the following raw materials in percentage by weight:
60-75% of fructose syrup, 7-10% of saccharified starch, 2.5-4% of xylitol and 15-26% of ethylene glycol;
the cross-linking agent is Benzoyl Peroxide (BPO), which is 1 per mill of the weight of the base component.
Among them, Fructose syrup is also called high Fructose corn syrup (Fructose Com Syrups) or isomeric syrup. At present, fructose syrup is mainly applied to the soft drink industry and is used as one of base materials of soft drinks; in addition, the method also relates to the fields of wine industry, daily chemical industry, household flavoring agents and the like, but no report about the application of fructose syrup in preparing a binding agent for three major steel-making and continuous casting and magnesia carbon brick production is found.
The saccharified starch is prepared by the following method:
mixing starch and water according to the proportion of 1g (4-6) ml, and carrying out size mixing to obtain starch size; adding neutral protease into the starch slurry, wherein the enzyme activity of the neutral protease is 10000U/g, the addition amount of the neutral protease is 0.05 percent of the weight of the starch, and keeping the temperature at 30-40 ℃ for 10-20 min; then adding high temperature resistant alpha-amylase, the adding amount of which is 0.08 percent of the weight of the starch, stirring uniformly, then pumping the mixture into a liquefaction ejector, and keeping the temperature of 125 ℃ for 5min to obtain a liquefied liquid with the DE value of 16-18 percent;
flashing the liquefied liquid for 10s under the conditions of-0.06 Mpa and 100 ℃, adding the flashed liquefied liquid into a saccharification tank, adding saccharifying enzyme at the temperature of 60 ℃ and the pH value of 4.5-5.0, wherein the adding amount is 0.05 percent of the weight of the starch, and stirring for 24 hours to react to obtain the saccharified starch.
The neutral protease, the thermostable alpha-amylase and the saccharifying enzyme can be obtained commercially.
The saccharified starch prepared by the method is added with neutral protease for heat preservation treatment before liquefaction, so that the function of decomposing protein tightly combined with the starch can be enhanced, and the starch degradation is facilitated; the prepared saccharified starch has proper viscosity and good molding performance.
The invention discloses a bonding agent, which is prepared by mixing fructose syrup as a solvent, saccharified starch, xylitol and glycol in the above amount, wherein the saccharified starch, the xylitol and the glycol are mixed with the fructose syrup to form a mixture, and the mixture is subjected to a high-temperature heating treatment. In addition, the addition of the cross-linking agent is also very critical, and the components can stably exist by adding the cross-linking agent, so that the using effect of the bonding agent is effectively improved.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples and comparative examples of the present invention are conventional in the art and are commercially available.
Example 1: binding agent for producing three major parts of steel-making continuous casting and magnesia carbon brick
1. Comprises the following components:
the bonding agent is prepared from a basic component and a cross-linking agent; wherein:
the base component comprises the following raw materials in percentage by weight:
69% of fructose syrup, 7.5% of saccharified starch, 3.5% of xylitol and 20% of ethylene glycol;
the cross-linking agent is Benzoyl Peroxide (BPO), and the addition amount is 1 per mill of the weight of the base component.
2. The preparation method comprises the following steps:
mixing fructose syrup, saccharified starch, xylitol and ethylene glycol in proportion to serve as basic components; and then adding a cross-linking agent into the basic component, and uniformly mixing to obtain the bonding agent.
Example 2: binding agent for producing three major parts of steel-making continuous casting and magnesia carbon brick
1. Comprises the following components:
the bonding agent is prepared from a basic component and a cross-linking agent; wherein:
the base component comprises the following raw materials in percentage by weight:
60% of fructose syrup, 10% of saccharified starch, 4% of xylitol and 26% of ethylene glycol;
the cross-linking agent is Benzoyl Peroxide (BPO), and the addition amount is 1 per mill of the weight of the base component.
2. The preparation method comprises the following steps: the same as in example 1.
Example 3: binding agent for producing three major parts of steel-making continuous casting and magnesia carbon brick
1. Consists of the following components:
the bonding agent is prepared from a basic component and a cross-linking agent; wherein:
the base component comprises the following raw materials in percentage by weight:
75% of fructose syrup, 7% of saccharified starch, 2.5% of xylitol and 15.5% of ethylene glycol;
the cross-linking agent is Benzoyl Peroxide (BPO), and the addition amount is 1 per mill of the weight of the base component.
2. The preparation method comprises the following steps: the same as in example 1.
Comparative example 1: preparation of Binders
1. Consists of the following components:
the composite material consists of the following raw materials in percentage by weight:
69% of fructose syrup, 7.5% of saccharified starch, 3.5% of xylitol and 20% of ethylene glycol.
2. The preparation method comprises the following steps:
and mixing the fructose syrup, the saccharified starch, the xylitol and the ethylene glycol in proportion to obtain the binding agent A.
Comparative example 2: preparation of Binders
1. Consists of the following components:
the bonding agent is prepared from a basic component and a cross-linking agent; wherein:
the base component comprises the following raw materials in percentage by weight:
69% of fructose syrup, 3.5% of xylitol and 27.5% of ethylene glycol;
the cross-linking agent is Benzoyl Peroxide (BPO), and the addition amount is 1 per mill of the weight of the base component.
2. The preparation method comprises the following steps:
mixing fructose syrup, xylitol and ethylene glycol in proportion to serve as basic components; and adding a cross-linking agent into the basic component, and uniformly mixing to obtain the bonding agent B.
Comparative example 3: preparation of Binders
1. Consists of the following components:
the bonding agent is prepared from a basic component and a cross-linking agent; wherein:
the base component comprises the following raw materials in percentage by weight:
69% of fructose syrup, 7.5% of saccharified starch and 23.5% of ethylene glycol;
the crosslinking agent is dicumyl peroxide (DCP), and the addition amount is 1 per mill of the weight of the basic component.
2. The preparation method comprises the following steps:
mixing fructose syrup, saccharified starch and glycol in proportion to serve as basic components; and adding a cross-linking agent into the basic component, and uniformly mixing to obtain the bonding agent C.
Comparative example 4: preparation of Binders
1. Consists of the following components:
60% of phenolic resin, 20% of furfural resin and 20% of ethanol.
2. The preparation method comprises the following steps:
and uniformly mixing the phenolic resin, the furfural resin and the ethanol to prepare the binder D.
Application example 1: preparation of three major parts for steelmaking and continuous casting
The method is characterized in that alumina and graphite are used as raw materials, wherein the content of the alumina is 78%, and the content of the graphite is 22%. Adding 8 wt% of the bonding agent prepared in the example 1, mixing by a high-speed mixer, and carrying out static pressure forming to obtain a semi-finished product; and (3) carrying out heat treatment on the semi-finished product in an atmosphere protection treatment furnace to prepare three steel-making continuous casting pieces 1.
For comparison, three large steel-making continuous casting pieces a, three large steel-making continuous casting pieces B, three large steel-making continuous casting pieces C, and three large steel-making continuous casting pieces D were prepared as described above by replacing the added binder (prepared in example 1) with the binders prepared in comparative examples 1 to 4, respectively.
Application example 2: preparation of magnesia carbon brick
The magnesia aggregate (55 wt%), the waste magnesia carbon brick reclaimed material (30 wt%), boron carbide (5 wt%) and graphite (10 wt%) are used as raw materials, the binder prepared in the embodiment 1 with the weight of 2.8 wt% of the raw materials is added, the raw materials are mixed and pressed into a green brick, and then the green brick is heated to prepare the magnesia carbon brick.
For comparison, a magnesia carbon brick a, a magnesia carbon brick B, a magnesia carbon brick C, and a magnesia carbon brick D were produced by the above-described method, with the added binder (produced in example 1) replaced with the binder produced in comparative examples 1 to 4, respectively.
The method for testing the performances of the magnesia carbon bricks prepared in the three steelmaking continuous casting pieces prepared in the application example 1 and the magnesia carbon bricks prepared in the application example 2 are tested by referring to a GB/T2997-2000 compact setting refractory product volume density and apparent porosity test method, a GB/T3001-2007 refractory material normal-temperature breaking strength test method, a GB/T3002-2004 refractory material high-temperature breaking strength test method and a GB/T30873-2014 refractory material thermal shock resistance test method, and comprises the following steps: the detection results of the three main parts of the steel-making continuous casting are shown in the table 1, and the detection results of the magnesia carbon brick are shown in the table 2.
Table 1: detection results of three major parts of steel-making and continuous casting
Table 2: detection result of magnesia carbon brick
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (2)
1. The bonding agent for three-piece production of steelmaking and continuous casting is characterized in that the bonding agent is prepared from a base component and a cross-linking agent;
the base component comprises the following raw materials in percentage by weight:
69% of fructose syrup, 7.5% of saccharified starch, 3.5% of xylitol and 20% of ethylene glycol;
the cross-linking agent is benzoyl peroxide, and the cross-linking agent is 1 per mill of the weight of the basic component;
the saccharified starch is prepared by the following method:
mixing starch and water according to the proportion of 1g (4-6) ml, and mixing to obtain starch slurry; adding neutral protease into the starch slurry, wherein the enzyme activity of the neutral protease is 10000U/g, the addition amount of the neutral protease is 0.05 percent of the weight of the starch, and keeping the temperature at 30-40 ℃ for 10-20 min; then adding high temperature resistant alpha-amylase, the adding amount of which is 0.08 percent of the weight of the starch, stirring uniformly, then pumping the mixture into a liquefaction ejector, and keeping the ejection temperature at 125 ℃ for 5min to obtain a liquefaction liquid with the DE value of 16-18 percent;
flashing the liquefied liquid for 10s at-0.06 Mpa and 100 ℃, adding the flashed liquefied liquid into a saccharification tank, adding saccharifying enzyme at 60 ℃ and pH4.5-5.0, wherein the adding amount is 0.05 percent of the weight of the starch, and stirring for reacting for 24h to obtain the saccharified starch;
the binding agent is prepared by the following steps:
mixing fructose syrup, saccharified starch, xylitol and ethylene glycol in proportion to serve as basic components; and then adding a cross-linking agent into the basic component, and uniformly mixing to obtain the bonding agent.
2. The three steel-making continuous casting large parts are characterized by being prepared by the following steps:
taking alumina and graphite as raw materials, wherein the content of the alumina is 78 percent, the content of the graphite is 22 percent, adding the bonding agent of claim 1 accounting for 8 weight percent of the weight of the raw materials, mixing by a high-speed mixer, and carrying out static pressure forming to obtain a semi-finished product; and (4) carrying out heat treatment on the semi-finished product in an atmosphere protection treatment furnace to prepare three continuous casting pieces for steelmaking.
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| CN111285696B (en) * | 2020-03-30 | 2022-03-29 | 艾文斯（焦作）冶金材料有限责任公司 | Molten aluminum refractory material runner repairing agent and preparation method thereof |
| CN111574231A (en) * | 2020-05-27 | 2020-08-25 | 大石桥市宝鼎耐火材料有限公司 | Environment-friendly magnesia carbon brick and preparation method thereof |
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