CN102127197A - Preparation method for phenolic resin for magnesia-carbon brick - Google Patents
Preparation method for phenolic resin for magnesia-carbon brick Download PDFInfo
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- CN102127197A CN102127197A CN 201010568441 CN201010568441A CN102127197A CN 102127197 A CN102127197 A CN 102127197A CN 201010568441 CN201010568441 CN 201010568441 CN 201010568441 A CN201010568441 A CN 201010568441A CN 102127197 A CN102127197 A CN 102127197A
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Abstract
The invention discloses a preparation method of phenolic resin for a magnesia-carbon brick. The method comprises the following steps of: (1) adding phenol, formaldehyde and an alkaline catalyst into a reaction kettle in the mass ratio of 1.0:(1.1-1.5):(0.01-0.03), raising the temperature to 60-90 DEG C and preserving heat for 1-4 hours; (2) adding papermaking waste liquor and alcohol substances into the reaction kettle and stirring uniformly, wherein the weight of the papermaking waste liquor is 10-20 percent of that of phenol, and the weight of the alcohol substances is 2-5 percent of that of the phenol; and (3) performing vacuum distillation on a uniform mixture obtained in the step (2) at the temperature between 60 DEG C and 90 DEG C until the viscosity of the uniform mixture is between 3,000 MPa.s per 25 DEG C and 25,0000 MPa.s per 25 DEG C. The magnesia-carbon brick obtained by mixing the phenolic resin prepared with the method with magnesia aggregate, magnesia fine powder and graphite and molding has high mechanical property, high compressive strength and high high-temperature breaking strength; meanwhile, the phenolic resin has low preparation cost, so that the production cost of the magnesia carbon brick is greatly lowered.
Description
Technical field
The present invention relates to the phenolic resins field, especially be used as the preparation method of the resol of magnesium carbon refractory brick wedding agent.
Background technology
The magnesium carbon refractory is to be the refractory materials of main component with magnesium oxide and carbon.Have good resistance to slag corrosion, slag penetration, thermal shock resistance and thermal conductivity.Apparent porosity is 3%～10%.Be mainly used in furnace lining, the tap hole of steel-making oxygen converter, superpower electric furnace furnace wall focus position, and external refining inner lining of furnace, steel teeming ladle slag lining etc.General to adopt highly-purity magnesite powder, carbon materials (comprising graphite) and tar-bitumen or resin etc. be raw material, after batching, hot mixed, moulding, forms through roasting about 300 ℃ or more than 1000 ℃ again.
The applicating history of magnesium carbon refractory is long, has wide range of applications, and especially magnesia carbon brick has obtained good application at aspects such as converter, electric furnace, ladle and external refinings.Make the used wedding agent of magnesia carbon brick and be generally resol, resol is to be formed by phenols and aldehyde condensation polymer reaction, be starting material with phenol and formaldehyde generally speaking, because the phenol cost of resol that directly caused on the high side is higher, 15000 yuan/ton of prices.Though the magnesia carbon brick quality that common resol is made on the market is better, because common resol price is higher, has also restricted the fast development of magnesia carbon brick, it is very necessary therefore developing a kind of resol of magnesia carbon brick cheaply.
Summary of the invention
The present invention is directed to deficiency, propose the preparation method of a kind of magnesia carbon brick with resol, the magnesia carbon brick that the resol that employing obtains is produced has the favorable mechanical performance, reduces production costs significantly simultaneously.
In order to realize the foregoing invention purpose, the invention provides following technical scheme: a kind of magnesia carbon brick preparation method of resol may further comprise the steps:
1., phenol, formaldehyde and basic catalyst pressed amount of substance add in the reactor than 1.0: 1.1～1.5: 0.01～0.03, be warming up to 60～90 ℃, constant temperature 1～4 hour;
2., in reactor, add and account for the papermaking wastewater of phenol weight 10～20% and 2～5% alcohols material, stir;
3., 60～90 ℃ of following vacuum distilling steps homomixture 2., to the viscosity of homomixture be 3000～25000MPas/25 ℃.
Preferably, step 1. the neutral and alkali catalyzer be selected from one or more of sodium hydroxide, calcium hydroxide, yellow soda ash, calcium oxide.
Preferably, the 2. middle alcohols of step is selected from dibasic alcohol or trivalent alcohol.
Preferably, described dibasic alcohol is ethylene glycol or Diethylene Glycol.
Preferably, described trivalent alcohol is a glycerol.
Preferably, step 3. in the pressure of vacuum distilling be 0.01～0.06MPa.
A kind of magnesia carbon brick resol adopts aforesaid preparation method to be prepared from.
A kind of magnesia carbon brick, by above-mentioned resol, with magnesia aggregate, magnesia powder and graphite mixing, moulding and making.
Compared with prior art, the present invention adds papermaking wastewater and alcohols material in the resol of ordinary method preparation, wherein since papermaking wastewater in 30～50wt% be xylogen, and xylogen has the structure similar to resol, therefore can partly substitute the production that phenol is used for resol.After in phenolic resin system, adding papermaking wastewater, under alkaline environment, the active site number of xylogen increases to a certain extent to some extent, and further participate in polyreaction between phenol and the formaldehyde, not only improve the solid content and the carbon residue rate of resol, and also improved the cost performance of resol to a certain extent.And the alcohols material that adds, the viscosity that is used for regulating prepared resol; Because the boiling point of monohydroxy-alcohol is lower, what the present invention used is high boiling dibasic alcohol or trivalent alcohol.
Adopt the resol of the present invention's preparation, mix with magnesia aggregate, magnesia powder, graphite, the magnesia carbon brick that obtains of forming processes then, has the favorable mechanical performance: compressive strength and high temperature break resistant intensity, cost of manufacture owing to resol of the present invention is low simultaneously, thereby can reduce the production cost of magnesia carbon brick significantly.
Embodiment
Describe the present invention below in conjunction with specific embodiment, the description of this part only is exemplary and explanatory, should any restriction not arranged to protection scope of the present invention.
Embodiment 1
Phenol, formaldehyde, sodium hydroxide are pressed amount of substance to add in the reactor than 1: 1.5: 0.01, heated and stirred to 60 ℃, constant temperature is after 4 hours in this temperature range, 60 ℃ of papermaking wastewaters that add phenol weight 20%, behind the constant temperature 3 hours, the ethylene glycol that adds phenol weight 3%, dewater under 60 ℃ and the 0.01MPa to resin viscosity be 4300MPas/25 ℃.
The resol solid content that present embodiment is produced is 75～82%, and the carbon residue rate is 45～48%, and moisture is 4～6%, and free phenol is 7～10%.
Embodiment 2
Phenol, formaldehyde, calcium hydroxide are pressed amount of substance to add in the reactor than 1: 1.3: 0.02, heated and stirred to 70 ℃, constant temperature is after 3 hours in this temperature range, 70 ℃ of papermaking wastewaters that add phenol weight 10%, behind the constant temperature 2 hours, the glycerol that adds phenol weight 2%, vacuum hydro-extraction to resin viscosity is 10000mPas/25 ℃ under 70 ℃ and the 0.06MPa.
The resol solid content that present embodiment is produced is 76～83%, and the carbon residue rate is 45～50%, and moisture is 4～6%, and free phenol is 7～10%.
Embodiment 3
Phenol, formaldehyde, sodium hydroxide are pressed amount of substance to add in the reactor than 1: 1.1: 0.03, heated and stirred to 80 ℃, constant temperature is after 2 hours in this temperature range, 80 ℃ of papermaking wastewaters that add phenol weight 15%, behind the constant temperature 1 hour, vacuum hydro-extraction to resin viscosity is 7000MPas/25 ℃ under the Diethylene Glycol that adds phenol weight 5%, 80 ℃ and 0.04MPa.
The resol solid content that present embodiment is produced is 75～83%, and the carbon residue rate is 45～49%, and moisture is 4～6%, and free phenol is 7～10%.
The comparative example
With common resol on the foregoing description 1, embodiment 2 or embodiment 3 prepared resol and the market, respectively as the wedding agent of coal dress, with be pressed into adobe after brick-making raw materials such as magnesia aggregate, magnesia powder, graphite mix, make magnesia carbon brick through heat drying again, compare experiment, the results are shown in Table 1 and table 2.
The composition of table 1 magnesia carbon brick
The magnesia carbon brick comparative test result of the different wedding agents of table 2
As can be seen from Table 1, above-mentioned magnesia carbon brick is the wedding agent difference, and other components, content are all the same; These four groups of magnesia carbon bricks are compared the detection test, and gained is the result listed by table 2.By table 2 result as can be known, under the identical situation of brickmaking condition, the magnesia carbon brick of producing of the present invention is similar with the magnesia carbon brick detected result that common resol is produced, and can keep former good performance, but cost reduces greatly.Since 15000 yuan/ton of common resol prices, and resol of the present invention carries out utilization of waste material owing to the employing papermaking wastewater, and cost value is 13000 yuan/ton.
It below only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a magnesia carbon brick may further comprise the steps with the preparation method of resol:
1., phenol, formaldehyde and basic catalyst pressed amount of substance add in the reactor than 1.0: 1.1～1.5: 0.01～0.03, be warming up to 60～90 ℃, constant temperature 1～4 hour;
2., in reactor, add and account for the papermaking wastewater of phenol weight 10～20% and 2～5% alcohols material, stir;
3., 60～90 ℃ of following vacuum distilling steps homomixture 2., to the viscosity of homomixture be 3000～25000MPas/25 ℃.
2. preparation method as claimed in claim 1 is characterized in that: step 1. neutral and alkali catalyzer is selected from one or more of sodium hydroxide, calcium hydroxide, yellow soda ash, calcium oxide.
3. preparation method as claimed in claim 1 is characterized in that: the 2. middle alcohols of step is selected from dibasic alcohol or trivalent alcohol.
4. preparation method as claimed in claim 3 is characterized in that: described dibasic alcohol is ethylene glycol or Diethylene Glycol.
5. preparation method as claimed in claim 3 is characterized in that: described trivalent alcohol is a glycerol.
6. preparation method as claimed in claim 1 is characterized in that: the step 3. pressure of middle vacuum distilling is 0.01～0.06MPa.
7. a magnesia carbon brick resol adopts preparation method as claimed in claim 1 to be prepared from.
8. magnesia carbon brick, by resol as claimed in claim 7, with magnesia aggregate, magnesia powder and graphite mixing, moulding and making.
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| CN 201010568441 CN102127197B (en) | 2010-12-01 | 2010-12-01 | Preparation method for phenolic resin for magnesia-carbon brick |
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| CN 201010568441 CN102127197B (en) | 2010-12-01 | 2010-12-01 | Preparation method for phenolic resin for magnesia-carbon brick |
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| CN102127197A true CN102127197A (en) | 2011-07-20 |
| CN102127197B CN102127197B (en) | 2012-07-04 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276957A (en) * | 2011-08-02 | 2011-12-14 | 山东圣泉化工股份有限公司 | Phenolic resin for refractory bricks and preparation method thereof |
| CN103030759A (en) * | 2012-12-19 | 2013-04-10 | 山东圣泉化工股份有限公司 | Lignin phenol resin prepolymer and preparation method thereof, lignin phenol resin and preparation method thereof |
| CN103183798A (en) * | 2011-12-29 | 2013-07-03 | 财团法人工业技术研究院 | Method for producing phenolic resin, resin material, and method for producing resin molded material |
| CN104628404A (en) * | 2015-03-02 | 2015-05-20 | 新乡市熔鑫耐材有限责任公司 | Preparation method of carbon-carbon combined refractory material binding agent |
| CN105503212A (en) * | 2015-12-21 | 2016-04-20 | 江苏苏嘉集团新材料有限公司 | Magnesia carbon brick and preparation method thereof |
| US9328188B2 (en) | 2011-12-29 | 2016-05-03 | Industrial Technology Research Institute | Method for preparing phenol-formaldehyde resins, resin materials and method for preparing resin molding materials |
| CN105670217A (en) * | 2016-01-27 | 2016-06-15 | 长兴华晨化工有限公司 | Production technology of novel special resin for magnesite-dolomite carbon bricks |
| CN108863247A (en) * | 2017-10-13 | 2018-11-23 | 济宁明升新材料有限公司 | A kind of foam water adobe for building and preparation method thereof |
| CN111087563A (en) * | 2019-12-25 | 2020-05-01 | 上海昶法新材料有限公司 | Modified phenolic resin, preparation method and refractory material containing modified phenolic resin |
| CN111647699A (en) * | 2020-07-04 | 2020-09-11 | 中冶南方邯郸武彭炉衬新材料有限公司 | Carbon block for hearth of blast furnace bottom and manufacturing method thereof |
| CN113728053A (en) * | 2018-12-27 | 2021-11-30 | 苏扎诺有限公司 | Novolac-type phenol resin, method for synthesizing same, and use thereof |
| CN114133246A (en) * | 2021-12-01 | 2022-03-04 | 湖南湘瓷科艺有限公司 | Based on carbon-based and ceramic-based composites |
| CN117362056A (en) * | 2023-12-07 | 2024-01-09 | 山东海泰高温材料有限公司 | Preparation method and application of magnesia carbon brick for steel ladle |
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| US3463747A (en) * | 1965-05-10 | 1969-08-26 | Westvaco Corp | Dicyandiamide modified resin binders |
| CN1632030A (en) * | 2004-08-03 | 2005-06-29 | 曲韵丰 | Composite phenolic resin glue producing method |
| CN101348698A (en) * | 2008-09-12 | 2009-01-21 | 中国林业科学研究院林产化学工业研究所 | Preparation of alkali lignin-phenolic composite adhesive for timber industry |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276957A (en) * | 2011-08-02 | 2011-12-14 | 山东圣泉化工股份有限公司 | Phenolic resin for refractory bricks and preparation method thereof |
| CN103183798A (en) * | 2011-12-29 | 2013-07-03 | 财团法人工业技术研究院 | Method for producing phenolic resin, resin material, and method for producing resin molded material |
| CN103183798B (en) * | 2011-12-29 | 2015-07-22 | 财团法人工业技术研究院 | Method for producing phenolic resin, resin material, and method for producing resin molded material |
| US9328188B2 (en) | 2011-12-29 | 2016-05-03 | Industrial Technology Research Institute | Method for preparing phenol-formaldehyde resins, resin materials and method for preparing resin molding materials |
| CN103030759A (en) * | 2012-12-19 | 2013-04-10 | 山东圣泉化工股份有限公司 | Lignin phenol resin prepolymer and preparation method thereof, lignin phenol resin and preparation method thereof |
| CN103030759B (en) * | 2012-12-19 | 2015-01-14 | 山东圣泉新材料股份有限公司 | Lignin phenol resin prepolymer and preparation method thereof, lignin phenol resin and preparation method thereof |
| CN104628404A (en) * | 2015-03-02 | 2015-05-20 | 新乡市熔鑫耐材有限责任公司 | Preparation method of carbon-carbon combined refractory material binding agent |
| CN104628404B (en) * | 2015-03-02 | 2016-08-24 | 新乡市炬能耐材有限公司 | A kind of preparation method of carbon-to-carbon combined fire-resistant material bonding agent |
| CN105503212B (en) * | 2015-12-21 | 2018-07-20 | 江苏苏嘉集团新材料有限公司 | A kind of magnesia carbon brick and preparation method thereof |
| CN105503212A (en) * | 2015-12-21 | 2016-04-20 | 江苏苏嘉集团新材料有限公司 | Magnesia carbon brick and preparation method thereof |
| CN105670217A (en) * | 2016-01-27 | 2016-06-15 | 长兴华晨化工有限公司 | Production technology of novel special resin for magnesite-dolomite carbon bricks |
| CN108863247A (en) * | 2017-10-13 | 2018-11-23 | 济宁明升新材料有限公司 | A kind of foam water adobe for building and preparation method thereof |
| CN113728053A (en) * | 2018-12-27 | 2021-11-30 | 苏扎诺有限公司 | Novolac-type phenol resin, method for synthesizing same, and use thereof |
| CN111087563A (en) * | 2019-12-25 | 2020-05-01 | 上海昶法新材料有限公司 | Modified phenolic resin, preparation method and refractory material containing modified phenolic resin |
| CN111647699A (en) * | 2020-07-04 | 2020-09-11 | 中冶南方邯郸武彭炉衬新材料有限公司 | Carbon block for hearth of blast furnace bottom and manufacturing method thereof |
| CN114133246A (en) * | 2021-12-01 | 2022-03-04 | 湖南湘瓷科艺有限公司 | Based on carbon-based and ceramic-based composites |
| CN117362056A (en) * | 2023-12-07 | 2024-01-09 | 山东海泰高温材料有限公司 | Preparation method and application of magnesia carbon brick for steel ladle |
| CN117362056B (en) * | 2023-12-07 | 2024-02-20 | 山东海泰高温材料有限公司 | Preparation method and application of magnesia carbon brick for steel ladle |
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| CN102127197B (en) | 2012-07-04 |
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