CN104193935A - Furan resin for cast steel and synthesis method thereof - Google Patents
Furan resin for cast steel and synthesis method thereof Download PDFInfo
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- CN104193935A CN104193935A CN201410434199.9A CN201410434199A CN104193935A CN 104193935 A CN104193935 A CN 104193935A CN 201410434199 A CN201410434199 A CN 201410434199A CN 104193935 A CN104193935 A CN 104193935A
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- cast steel
- furfuryl alcohol
- coupling agent
- furane resin
- formaldehyde
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Abstract
The invention relates to a furan resin for cast steel and a synthesis method thereof. The furan resin is characterized by comprising the following raw materials in percentage by mass: 70-80% of furfuryl alcohol, 9-15% of solid formaldehyde, 10-15% of phenol, 0.5-5.0% of urea, 0.2-0.5% of coupling agent and 2-5% of water. The solid formaldehyde is used instead of liquid formaldehyde in the synthesis process of the furan resin for cast steel, thereby reducing the sewage generated in the production process of the furan resin for cast steel; and the furan resin for cast steel has the characteristics of high strength, low viscosity, favorable molding-sand property and the like.
Description
Technical field
The invention belongs to a kind of furane resin and synthetic method thereof, particularly relate to furane resin and synthetic method thereof for a kind of cast steel.
Background technology
In sand mold casting, the feature such as it is high that self-hardening furan resin sand molding and core making has intensity, and dimensional precision is high, setting rate is fast, production efficiency is high, molding sand collapsibility is good, labour intensity is low, in producing at present, application is very extensive.Furane resin are condensation resins of application quantity maximum in Foundry Production up to now, and annual consumption has reached more than 500,000 tons.The furfuryl alcohol that furane resin refer to have furan nucleus is done the general name of the resene of raw material production, and it is cured as insoluble and not molten solid substance in acidic medium, and the main raw material of producing furane resin is furfuryl alcohol, formaldehyde and urea.First, by urea and formaldehyde, under alkaline condition, carry out addition reaction, generate monomethylolurea and dimethylolurea.Hydroxymethyl derivative carries out condensation reaction with furfuryl alcohol under acidic conditions, after vacuum hydro-extraction, obtains furane resin.The water of deviating from during resin is synthetic, mainly from formaldehyde solution, is easy to be deviate from because boiling point is low at unreacted formaldehyde of vacuum hydro-extraction stage, and furfuryl alcohol is due to hydrogen bond effect simultaneously, and also easy and water azeotropic steams.Cause existing in water a large amount of furfuryl alcohols and a small amount of formaldehyde.If this waste water direct oxidation will consume a large amount of oxygenants, if the direct biochemical treatment of this waste water will directly make bacterial classification inactivation.
At present, the processing of furan resin waste water is generally adopted to the methods such as burning, High Dose Oxygen agent oxide treatment, energy consumption is large, and expense is high, and in waste water, active substance is underutilized.In addition, furane resin Free-formaldehyde content is an important technology index weighing resin, if resin Free-formaldehyde too high levels, when the operations such as mulling, moulding, sclerosis, formaldehyde can discharge, both contaminate environment, endangered again the healthy of operator.
Relevant furane resin and synthetic method thereof, we retrieve with Publication about Document:
1, Chinese patent, title: a kind of production technique application (patent) number of furan resin for casting: CN 201110407561.X open (bulletin) number: CN 102516482A applies for (patent right) people: Ningxia Gongxiang Group Co., Ltd. address: No. 199, concentric South Road, Xixia District, Yinchuan City, Ningxia Hui Autonomous Region invention (design) people: Jin Yi; He Long; Yang Yang; Korean summary: a kind of production technique of furan resin for casting, is characterized in that: it comprises the steps: to feed in raw material, heat temperature raising, dewater, open steam valve, is warming up to 80-108 ℃ in 20-30 minute, be incubated 60-90 minute, discharging and packing put in storage; Technique provided by the invention can provide a kind of low content of free formaldehyde, high-intensity product, and production link is without the environmental protection of three wastes generation.
2, Chinese patent, title: a kind of furan resin for casting and preparation method thereof application (patent) number: 201210377741.2 open (bulletin) number: CN102863600A application (patent right) people: Shengquan Group Co. Ltd., Jinan, address: the Diao Zhen of Zhangqiu City, Jinan City, Shandong Province industrial economy development area, invention (design) people: Zhu Jianxun; Liu Zhao recommends; Sun Yongfeng, summary: a kind of furan resin for casting and preparation method thereof, it mainly forms by each composition of following weight parts is synthetic: 15-35 part formaldehyde, 5-10 part urea, 60-90 part furfuryl alcohol, 5-40 part xylogen.The present invention is by utilizing lignin modification furfuryl alcohol, when reducing costs, its free formaldehyde content decrease to some degree, simultaneously its just intensity and whole intensity are also improved to some extent.
3, Chinese patent, title: a kind of low-cost high-strength furane resin and preparation method thereof application (patent) number: CN201210398634.8 open (bulletin) number: CN 102875757A applies for (patent right) people: Chongqing Hao Jiang refractory materials limited liability company address: No. 200, great Ping village, Tong Guanyi town, Jiulongpo District, Chongqing City, invention (design) people: Liu Wei, summary: a kind of low-cost high-strength furane resin and preparation method thereof, , its formula and weight percentage thereof consist of: 36.5% formaldehyde 12%-30%, urea 3%-12%, furfuryl alcohol 35%-70%, trimeric cyanamide 0.5%-5%, industry Xylitol mother liquor 0.1%-25% and coupling agent 0.2%-0.8%, comprise the following steps: formaldehyde alkali reaction, urea alkali reaction, furfuryl alcohol acid-reaction, vacuum hydro-extraction and discharging.The invention has the beneficial effects as follows: can obviously reduce the consumption of furfuryl alcohol and reduce discharge of wastewater, thereby realizing the effect reducing production costs with energy consumption.
Although the furane resin of above-mentioned document and synthetic method thereof can be synthesized the furane resin of casting use, in raw material, all adopting concentration is the liquid formaldehyde of 37% left and right, moisture 63% in formaldehyde solution, in polycondensation process, also will generate a certain amount of water.Therefore in the building-up process of resin, need to slough a large amount of processing wastewaters, in waste water, contain a large amount of free formaldehydes, methyl alcohol, the methyl small organic molecule such as mutter, COD value, up to tens thousand of, enter in water body and can cause very serious environmental pollution.
Summary of the invention
The object of this invention is to provide non-wastewater discharge in a kind of production process, synthetic furane resin free formaldehyde content is lower than 0.1%, furane resin and synthetic method thereof for the cast steel that specific tenacity is high, viscosity is low,
Technical scheme of the present invention is:
Cast steel furane resin, is characterized in that, its raw material and quality percentage composition are: furfuryl alcohol 70-80%, solid formaldehyde 9-15%, phenol 10-15%, urea 0.5-5.0%, coupling agent 0.2-0.5% and water 2-5%.
The synthetic method of furane resin for cast steel of the present invention, is characterized in that, comprises the following steps:
(1) phenol, water are added in reactor, start stirrer and stir, with basic catalyst, regulate pH value to 8.5-9.5;
(2) add urea, solid formaldehyde, adds steam and heats up, and keeps heating up 8 ℃ for every 5 minutes, is warming up to 90 ℃, insulation 50-70 minute;
(3) be cooled to below 80 ℃, add furfuryl alcohol, with basic catalyst, regulate pH value to 9.5-10.5;
(4) add steam intensification 105-115 ℃, insulation backflow 80-100 minute;
(5) be cooled to 50 ℃, add furfuryl alcohol and coupling agent, after stirring, obtain finished product.
Above-described solid formaldehyde is the paraformaldehyde of low polymerization degree, and content is 90.0-99.9%.
The 40%-50% that the weight percentage of the furfuryl alcohol adding in above-described step (3) forms for formula, the remaining part of furfuryl alcohol during the furfuryl alcohol amount that described step (5) adds forms for filling a prescription.
Above-described basic catalyst is one or more in sodium hydroxide, potassium hydroxide, trimeric cyanamide, vulkacit H.
Above-described coupling agent is silane coupling agent, for one or more in γ-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, silane coupling agent X-602, silane coupling agent Y-603.
Above-described cast steel can also add the polyvinyl alcohol of raw material total amount 0.1-0.5% by furane resin building-up process, polyvinyl alcohol is a kind of macromolecular compound with great amount of hydroxy group, can obtain polyvinyl alcohol hemiacetal and polyvinyl acetal with formaldehyde reaction, polyvinyl alcohol and polyvinyl formal itself have adhesiveproperties, make furane resin have good cementability.In addition, the part polyethylene alcohol that does not participate in reaction will become the trapping agent of formaldehyde, makes the free formaldehyde content in furane resin be reduced to 0.005%.
The substantive distinguishing features that the present invention is outstanding and significant progress are:
1, the synthetic liquid formaldehyde of using of general furane resin, because water content in liquid formaldehyde reaches 63%, also produces water in building-up process, therefore need to slough unnecessary moisture.Cast steel of the present invention is with adopting solid formaldehyde to replace liquid formaldehyde in furane resin building-up process, reduced the link of dewatering in building-up process, not only fundamentally solved the difficult problem that former technique produces contaminated wastewater, and reduce the required time of dehydration, 150 yuan/ton of the energy consumptions that reducing dewaters produces, reduce discharge of wastewater 180kg/ ton, and product performance improve 12%, reach environmental protection, energy-conservation, the object that increases benefit, there is significant society and economic benefit.
2, cast steel of the present invention, with adding coupling agent in furane resin building-up process, is greatly improved the intensity of resin, more than 24h intensity reaches 2.6MPa, can reduce the add-on of resin, thereby reduces casting cost.
3, with furane resin, to have viscosity low for cast steel of the present invention, is convenient to metering, easily mulling, and sand fluidity is good; Specific tenacity is high, can reduce resin amount, reduces production costs, simultaneously favourable raising casting quality.
4, cast steel of the present invention is with furane resin free formaldehyde content lower than 0.1%, and in production process, smell is little, has improved workman's working conditions, has reduced environmental pollution.
5, cast steel of the present invention is good by the molding sand collapsibility of furane resin, reduces and produces rear sand removal workload, improve working efficiency, and the casting dimension accuracy of producing is high, clear-cut, any surface finish.
embodiment 1
By furfuryl alcohol 780kg, solid formaldehyde 91kg, phenol 100kg, urea 6.5kg, silane coupling agent 2kg and water 20.5kg, through following steps, make:
(1) phenol, water are added in reactor, start stirrer and stir, with sodium hydroxide, regulate pH value to 8.5-9.5;
(2) add urea, solid formaldehyde, adds steam and heats up, and keeps heating up 8 ℃ for every 5 minutes, is warming up to 90 ℃, is incubated 50 minutes;
(3) be cooled to below 80 ℃, add furfuryl alcohol, with sodium hydroxide, regulate pH value to 9.5-10.5;
(4) add steam intensification 105-115 ℃, insulation backflow 80-100 minute;
(5) be cooled to 50 ℃, add furfuryl alcohol and silane coupling agent, after stirring, obtain finished product.
Described solid formaldehyde is the paraformaldehyde of low polymerization degree, and content is 90.0%.
The weight percentage of the furfuryl alcohol adding in described step (3) is 40% of formula composition, the remaining part of furfuryl alcohol during the furfuryl alcohol amount that described step (5) adds forms for filling a prescription.
embodiment 2
By furfuryl alcohol 712kg, solid formaldehyde 107kg, phenol 120kg, urea 11kg, silane coupling agent X-602 and γ-aminopropyl triethoxysilane 5kg, water 45kg, through following steps, make:
(1) phenol, water are added in reactor, start stirrer and stir, with potassium hydroxide, regulate pH value to 8.5-9.5;
(2) add urea, solid formaldehyde, adds steam and heats up, and keeps heating up 8 ℃ for every 5 minutes, is warming up to 90 ℃, is incubated 55 minutes;
(3) be cooled to below 80 ℃, add furfuryl alcohol, with potassium hydroxide, regulate pH value to 9.5-10.5;
(4) add steam intensification 105-115 ℃, insulation backflow 80-100 minute;
(5) be cooled to 50 ℃, add the mixture of furfuryl alcohol, silane coupling agent X-602 and γ-aminopropyl triethoxysilane, after stirring, obtain finished product.
Described solid formaldehyde is the paraformaldehyde of low polymerization degree, and content is 93.0%.
The weight percentage of the furfuryl alcohol adding in described step (3) is 45% of formula composition, the remaining part of furfuryl alcohol during the furfuryl alcohol amount that described step (5) adds forms for filling a prescription.
embodiment 3
By furfuryl alcohol 704kg, solid formaldehyde 115kg, phenol 130kg, urea 17.5kg, γ-methacryloxypropyl trimethoxy silane 4kg and water 30kg, through following steps, made:
(1) phenol, water are added in reactor, start stirrer and stir, with trimeric cyanamide and sodium hydroxide, regulate pH value to 8.5-9.5;
(2) add urea, solid formaldehyde, adds steam and heats up, and keeps heating up 8 ℃ for every 5 minutes, is warming up to 90 ℃, is incubated 60 minutes;
(3) be cooled to below 80 ℃, add furfuryl alcohol, with trimeric cyanamide and sodium hydroxide, regulate pH value to 9.5-10.5;
(4) add steam intensification 105-115 ℃, insulation backflow 80-100 minute;
(5) be cooled to 50 ℃, add furfuryl alcohol and γ-methacryloxypropyl trimethoxy silane, after stirring, obtain finished product.
Described solid formaldehyde is the paraformaldehyde of low polymerization degree, and content is 96.0%.
The weight percentage of the furfuryl alcohol adding in described step (3) is 48% of formula composition, the remaining part of furfuryl alcohol during the furfuryl alcohol amount that described step (5) adds forms for filling a prescription.
embodiment 4
By furfuryl alcohol 700kg solid formaldehyde 124.5kg, phenol 125kg, urea 21.5kg, coupling agent 4kg, polyvinyl alcohol 2kg and water 25kg, through following steps, made:
(1) phenol, water are added in reactor, start stirrer and stir, with sodium hydroxide, regulate pH value to 8.5-9.5;
(2) add urea, solid formaldehyde, adds steam and heats up, and keeps heating up 8 ℃ for every 5 minutes, is warming up to 90 ℃, is incubated 70 minutes;
(3) be cooled to below 80 ℃, add furfuryl alcohol, with sodium hydroxide, regulate pH value to 9.5-10.5;
(4) add steam intensification 105-115 ℃, insulation backflow 80-100 minute;
(5) be cooled to 50 ℃, add furfuryl alcohol and coupling agent, after stirring, obtain finished product.
Described solid formaldehyde is the paraformaldehyde of low polymerization degree, and content is 99.9%.
The weight percentage of the furfuryl alcohol adding in described step (3) is 50% of formula composition, the remaining part of furfuryl alcohol during the furfuryl alcohol amount that described step (5) adds forms for filling a prescription.
The technical indicator of furane resin for cast steel of the present invention:
Claims (6)
1. cast steel furane resin, is characterized in that, its raw material and quality percentage composition are: furfuryl alcohol 70-80%, solid formaldehyde 9-15%, phenol 10-15%, urea 0.5-5.0%, coupling agent 0.2-0.5% and water 2-5%.
2. the synthetic method of furane resin for cast steel claimed in claim 1, is characterized in that, comprises the following steps:
(1) phenol, water are added in reactor, start stirrer and stir, with basic catalyst, regulate pH value to 8.5-9.5;
(2) add urea, solid formaldehyde, adds steam and heats up, and keeps heating up 8 ℃ for every 5 minutes, is warming up to 90 ℃, insulation 50-70 minute;
(3) be cooled to below 80 ℃, add furfuryl alcohol, with basic catalyst, regulate pH value to 9.5-10.5;
(4) add steam intensification 105-115 ℃, insulation backflow 80-100 minute;
(5) be cooled to 50 ℃, add furfuryl alcohol and coupling agent, after stirring, obtain finished product.
3. the synthetic method of furane resin for a kind of cast steel according to claim 2, is characterized in that, the paraformaldehyde that described solid formaldehyde is low polymerization degree, and content is 90.0-99.9%.
4. the synthetic method of furane resin for a kind of cast steel according to claim 2, it is characterized in that: the 40%-50% that the weight percentage of the furfuryl alcohol adding in described step (3) forms for formula, the remaining part of furfuryl alcohol during the furfuryl alcohol amount that described step (5) adds forms for filling a prescription.
5. the synthetic method of furane resin for a kind of cast steel according to claim 2, is characterized in that: described basic catalyst is one or more in sodium hydroxide, potassium hydroxide, trimeric cyanamide, vulkacit H.
6. the synthetic method of furane resin for a kind of cast steel according to claim 2, is characterized in that, described coupling agent is silane coupling agent; For one or more in γ-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, silane coupling agent X-602, silane coupling agent Y-603.
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| CN201410434199.9A CN104193935A (en) | 2014-08-29 | 2014-08-29 | Furan resin for cast steel and synthesis method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037671A (en) * | 2015-07-15 | 2015-11-11 | 天津宁康科技有限公司 | Long-storage casting furan resin with low furfuryl alcohol content and preparation method thereof |
| CN105273151A (en) * | 2015-10-20 | 2016-01-27 | 苏州兴业材料科技股份有限公司 | Modified phenolic furan resin and binder adopting same |
| CN105669928A (en) * | 2016-03-07 | 2016-06-15 | 宁夏共享化工有限公司 | Non-dewatering production method of quick-hardening furan resin |
| CN106008871A (en) * | 2016-06-27 | 2016-10-12 | 霍山县忠福硅溶胶有限公司 | Furan resin and preparation method thereof |
| CN106977677A (en) * | 2017-04-07 | 2017-07-25 | 保定永强合成材料有限公司 | A kind of production technology of novel environment friendly furane resins |
| CN107383301A (en) * | 2017-08-30 | 2017-11-24 | 石家庄丰联精细化工有限公司 | A kind of cast steel furane resins and preparation method thereof |
| CN108889898A (en) * | 2018-06-06 | 2018-11-27 | 山东怡泰恒环保材料有限公司 | A kind of cast aluminium binder |
| CN109175220A (en) * | 2018-09-26 | 2019-01-11 | 保定永强合成材料有限公司 | A kind of efficient furan resin for casting and preparation method thereof |
| CN109467663A (en) * | 2018-12-19 | 2019-03-15 | 四川东树新材料有限公司 | One kind is based on diluted modified furan resin of mother liquor and preparation method thereof |
| CN110776612A (en) * | 2019-10-23 | 2020-02-11 | 广东省铸力铸材科技有限公司 | Furan resin and preparation method thereof |
| CN112222351A (en) * | 2020-09-28 | 2021-01-15 | 宁夏共享化工有限公司 | Furan resin and production method thereof |
| CN112409556A (en) * | 2020-11-27 | 2021-02-26 | 苏州兴业材料科技股份有限公司 | Method for preparing furan resin for casting from waste water |
| CN112759733A (en) * | 2020-12-24 | 2021-05-07 | 天津宁康科技有限公司 | Preparation method of low-odor high-strength environment-friendly furan resin |
| CN114106510A (en) * | 2021-12-22 | 2022-03-01 | 广东胜联新材料科技有限公司 | Production process of environment-friendly phenol urea formaldehyde modified furan resin |
| CN115109216A (en) * | 2022-07-06 | 2022-09-27 | 山东怡泰恒环保材料有限公司 | High-viscosity furan resin for casting and preparation method thereof |
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| CN102532450A (en) * | 2011-12-12 | 2012-07-04 | 宁夏共享集团有限责任公司 | Production method for quickly curing nitrogen-free furane resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102532450A (en) * | 2011-12-12 | 2012-07-04 | 宁夏共享集团有限责任公司 | Production method for quickly curing nitrogen-free furane resin |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037671B (en) * | 2015-07-15 | 2018-06-12 | 天津宁康科技有限公司 | A kind of low furfuryl alcohol content stores furan resin for casting and preparation method thereof long |
| CN105037671A (en) * | 2015-07-15 | 2015-11-11 | 天津宁康科技有限公司 | Long-storage casting furan resin with low furfuryl alcohol content and preparation method thereof |
| CN105273151A (en) * | 2015-10-20 | 2016-01-27 | 苏州兴业材料科技股份有限公司 | Modified phenolic furan resin and binder adopting same |
| CN105669928A (en) * | 2016-03-07 | 2016-06-15 | 宁夏共享化工有限公司 | Non-dewatering production method of quick-hardening furan resin |
| CN105669928B (en) * | 2016-03-07 | 2018-09-25 | 宁夏共享化工有限公司 | A kind of quick-hardening furane resins are not dehydrated production method |
| CN106008871A (en) * | 2016-06-27 | 2016-10-12 | 霍山县忠福硅溶胶有限公司 | Furan resin and preparation method thereof |
| CN106008871B (en) * | 2016-06-27 | 2018-07-31 | 霍山县忠福硅溶胶有限公司 | A kind of furane resins and preparation method thereof |
| CN106977677A (en) * | 2017-04-07 | 2017-07-25 | 保定永强合成材料有限公司 | A kind of production technology of novel environment friendly furane resins |
| CN107383301B (en) * | 2017-08-30 | 2019-11-01 | 石家庄丰联精细化工有限公司 | A kind of cast steel furane resins and preparation method thereof |
| CN107383301A (en) * | 2017-08-30 | 2017-11-24 | 石家庄丰联精细化工有限公司 | A kind of cast steel furane resins and preparation method thereof |
| CN108889898A (en) * | 2018-06-06 | 2018-11-27 | 山东怡泰恒环保材料有限公司 | A kind of cast aluminium binder |
| CN108889898B (en) * | 2018-06-06 | 2019-12-31 | 孙梓宁 | Adhesive for cast aluminum |
| CN109175220A (en) * | 2018-09-26 | 2019-01-11 | 保定永强合成材料有限公司 | A kind of efficient furan resin for casting and preparation method thereof |
| CN109467663A (en) * | 2018-12-19 | 2019-03-15 | 四川东树新材料有限公司 | One kind is based on diluted modified furan resin of mother liquor and preparation method thereof |
| CN109467663B (en) * | 2018-12-19 | 2021-03-02 | 四川东树新材料有限公司 | Modified furan resin based on mother liquor dilution and preparation method thereof |
| CN110776612A (en) * | 2019-10-23 | 2020-02-11 | 广东省铸力铸材科技有限公司 | Furan resin and preparation method thereof |
| CN112222351A (en) * | 2020-09-28 | 2021-01-15 | 宁夏共享化工有限公司 | Furan resin and production method thereof |
| CN112222351B (en) * | 2020-09-28 | 2022-08-05 | 宁夏共享化工有限公司 | Furan resin and production method thereof |
| CN112409556A (en) * | 2020-11-27 | 2021-02-26 | 苏州兴业材料科技股份有限公司 | Method for preparing furan resin for casting from waste water |
| CN112759733A (en) * | 2020-12-24 | 2021-05-07 | 天津宁康科技有限公司 | Preparation method of low-odor high-strength environment-friendly furan resin |
| CN114106510A (en) * | 2021-12-22 | 2022-03-01 | 广东胜联新材料科技有限公司 | Production process of environment-friendly phenol urea formaldehyde modified furan resin |
| CN115109216A (en) * | 2022-07-06 | 2022-09-27 | 山东怡泰恒环保材料有限公司 | High-viscosity furan resin for casting and preparation method thereof |
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Address after: 537005 the Guangxi Zhuang Autonomous Region Yulin Lu Chuan County northern industrial concentration zone Applicant after: GUANGXI LANKE NEW MATERIAL SCIENCE & TECHNOLOGY CO., LTD. Address before: 537005 North Industrial Park, Lu Chuan, the Guangxi Zhuang Autonomous Region, Yulin Applicant before: YULIN LANKE CASTING MATERIAL CO., LTD. |
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Application publication date: 20141210 |