CN112194875A - 一种褐煤基增韧酚醛泡沫及其制备方法 - Google Patents
一种褐煤基增韧酚醛泡沫及其制备方法 Download PDFInfo
- Publication number
- CN112194875A CN112194875A CN202011075926.9A CN202011075926A CN112194875A CN 112194875 A CN112194875 A CN 112194875A CN 202011075926 A CN202011075926 A CN 202011075926A CN 112194875 A CN112194875 A CN 112194875A
- Authority
- CN
- China
- Prior art keywords
- lignite
- phenolic foam
- carrying
- toughened phenolic
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0033—Use of organic additives containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
- C08J2361/10—Phenol-formaldehyde condensates
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
本发明公开了一种褐煤基增韧酚醛泡沫及其制备方法,属于低阶煤高值化利用领域。本发明酚醛泡沫以质量份数计包括褐煤基树脂100份;表面活性剂3‑8份;发泡剂5‑20份;固化剂8‑30份;所述褐煤基树脂是将褐煤在280‑350℃下进行乙醇解,所得可溶物部分以10‑50%的质量百分比替代苯酚,与甲醛进行缩聚制备而得。褐煤属于低阶煤,目前以燃烧发电为主,利用价值较低,本发明以褐煤醇解产物替代苯酚制备酚醛泡沫,既提高了褐煤的利用价值,又替代部分石油化工原料,降低了原材料成本,同时解决了常规酚醛泡沫韧性差的问题,因而具有良好的应用前景。
Description
技术领域
本发明属于低阶煤高值化利用领域。具体地说涉及一种用廉价的褐煤醇解产物替代部分石油化工原料苯酚,制备韧性增强的酚醛泡沫的方法。
背景技术
我国的褐煤资源丰富,保有储量达1300多亿吨,约占全国煤炭储量的13%。然而,大部分褐煤存在含氧量高、水分高、热值低、热稳定性差、易风化自燃等问题,以燃烧发电为主的传统能源利用方式效率低、污染大,并排放大量CO2。因此,亟待开发褐煤的高值化和低碳化利用技术。
酚醛泡沫由于具有优良的隔热和阻燃性能,被广泛用作高层建筑或交通运输的保温材料。当前,我国的酚醛树脂年产量超过100万吨,需要消耗大量的苯酚。工业上生产苯酚主要采用异丙苯法,而异丙苯主要来自于石油化工,造成苯酚的价格较高,且易受国际原油价格的影响而波动。因此,寻找石油基苯酚的替代品意义重大。鉴于褐煤富含酚羟基和芳醚键的结构特点,其解聚产物有望部分替代石油基苯酚制备酚醛泡沫。
发明内容
本发明的目的是要提供一种褐煤基增韧酚醛泡沫及其制备方法,为褐煤的高值化和低碳化利用提供一条新的途径。
为实现上述目的,本发明采用的技术方案为:
一种褐煤基增韧酚醛泡沫,其按质量份数计包括如下组分:
所述褐煤基树脂是将褐煤在280-350℃下进行乙醇解,所得可溶物部分以10-50%的质量百分比替代苯酚,与甲醛进行缩聚制备而得。
进一步的,所述褐煤基树脂的粘度为2-4Pa·s,固含量为70-85%。
进一步的,所述表面活性剂为吐温-80。
进一步的,所述固化剂为对甲苯磺酸、草酸、磷酸、盐酸中的一种或两种。
进一步的,所述发泡剂为低沸点烷烃类溶剂。
更进一步的,所述低沸点烷烃类溶剂为正戊烷、正己烷、环己烷以及石油醚30-60中的一种或两种。
本发明同时提供了上述褐煤基增韧酚醛泡沫的制备方法,具体包括如下步骤:
首先将褐煤在280-350℃下进行乙醇解,所得可溶物部分替代苯酚(10-50%),与甲醛进行缩聚制备褐煤基树脂,然后取该树脂100份,表面活性剂3-8份,发泡剂5-20份,固化剂8-30份,在室温下充分搅拌混合,在50-90℃下发泡10-90min,得到褐煤基增韧酚醛泡沫。
与现有技术相比,本发明具有以下技术效果:
1、本发明褐煤解聚采用的溶剂为乙醇,沸点低、无毒,易回收使用,且不使用氢气。
2、本发明褐煤乙醇解可溶物中富含烷基酚和脂肪酸乙酯,其制备的酚醛泡沫韧性较常规酚醛泡沫好。
3、褐煤属于低阶煤,目前以燃烧发电为主,利用价值较低,本发明以褐煤醇解产物替代苯酚制备酚醛泡沫,既提高了褐煤的利用价值,又替代部分石油化工原料,降低了原材料成本,同时解决了常规酚醛泡沫韧性差的问题,因而具有良好的应用前景。
具体实施方式
以下是本发明的具体实施例,对本发明的技术方案做进一步的描述,但本发明并不限于这些实施例。
实施例1
称取20g锡林郭勒褐煤,在高压釜中300℃下进行乙醇解反应2h,冷却至室温后,取出反应混合物,过滤,浓缩得乙醇解可溶物,乙醇解可溶物收率为57.4%。取8g褐煤乙醇解可溶物、12g苯酚、0.9gNaOH、6g去离子水,放入三口烧瓶加热至85℃,0.5h后逐滴加入甲醛水溶液31.2g,反应2h后,降至60℃,加乙酸调pH至6,浓缩得到褐煤基树脂,固含量为73%,粘度为3.5Pa·s。取20g树脂、2g正戊烷、0.6g吐温-80、5g对甲苯磺酸,放入一次性纸杯,迅速搅拌均匀,70℃下发泡固化0.5h,得褐煤基酚醛泡沫,密度为55kg/m3,导热系数为0.046W/(m·K),粉化率为5.3%,粉化率明显低于同条件下制备的纯酚醛泡沫(9.2%),这意味着酚醛泡沫的韧性得到显著增强。
实施例2
称取20g锡林郭勒褐煤,在高压釜中300℃下进行乙醇解反应2h,冷却至室温后,取出反应混合物,过滤,浓缩得乙醇解可溶物,乙醇解可溶物收率为57.4%。取6g褐煤乙醇解可溶物、14g苯酚、0.9gNaOH、6g去离子水,放入三口烧瓶加热至85℃,0.5h后逐滴加入甲醛水溶液31.2g,反应2h后,降至60℃,加乙酸调pH至6,浓缩得到褐煤基树脂,固含量为75%,粘度为3.2Pa·s。取20g树脂、2g正戊烷、0.6g吐温-80、5g对甲苯磺酸,放入一次性纸杯,迅速搅拌均匀,70℃下发泡固化0.5h,得褐煤基酚醛泡沫,密度为57kg/m3,导热系数为0.041W/(m·K),粉化率为6.8%,粉化率明显低于同条件下制备的纯酚醛泡沫(9.2%),这意味着酚醛泡沫的韧性得到显著增强。
实施例3
称取20g锡林郭勒褐煤,在高压釜中320℃下进行乙醇解反应2h,冷却至室温后,取出反应混合物,过滤,浓缩得乙醇解可溶物,乙醇解可溶物收率为59.7%。取8g褐煤乙醇解可溶物、12g苯酚、0.9gNaOH、6g去离子水,放入三口烧瓶加热至85℃,0.5h后逐滴加入甲醛水溶液31.2g,反应2h后,降至60℃,加乙酸调pH至6,浓缩得到褐煤基树脂,固含量为78%,粘度为3.7Pa·s。取20g树脂、2g正戊烷、0.6g吐温-80、5g对甲苯磺酸,放入一次性纸杯,迅速搅拌均匀,70℃下发泡固化0.5h,得褐煤基酚醛泡沫,密度为64kg/m3,导热系数为0.050W/(m·K),粉化率为5.0%,粉化率明显低于同条件下制备的纯酚醛泡沫(9.2%),这意味着酚醛泡沫的韧性得到显著增强。
实施例4
称取20g锡林郭勒褐煤,在高压釜中300℃下进行乙醇解反应2h,冷却至室温后,取出反应混合物,过滤,浓缩得乙醇解可溶物,乙醇解可溶物收率为57.4%。取8g褐煤乙醇解可溶物、12g苯酚、0.9gNaOH、6g去离子水,放入三口烧瓶加热至85℃,0.5h后逐滴加入甲醛水溶液31.2g,反应2h后,降至60℃,加乙酸调pH至6,浓缩得到褐煤基树脂,固含量为73%,粘度为3.5Pa·s。取20g树脂、3g正戊烷、0.6g吐温-80、6g对甲苯磺酸,放入一次性纸杯,迅速搅拌均匀,70℃下发泡固化0.5h,得褐煤基酚醛泡沫,密度为45kg/m3,导热系数为0.036W/(m·K),粉化率为7.3%,粉化率明显低于同条件下制备的纯酚醛泡沫(9.4%),这意味着酚醛泡沫的韧性得到显著增强。
实施例5
称取20g锡林郭勒褐煤,在高压釜中280℃下进行乙醇解反应2h,冷却至室温后,取出反应混合物,过滤,浓缩得乙醇解可溶物,乙醇解可溶物收率为50.8%。取8g褐煤乙醇解可溶物、12g苯酚、0.9gNaOH、6g去离子水,放入三口烧瓶加热至85℃,0.5h后逐滴加入甲醛水溶液31.2g,反应2h后,降至60℃,加乙酸调pH至6,浓缩得到褐煤基树脂,固含量为74%,粘度为3.7Pa·s。取20g树脂、3g正戊烷、0.6g吐温-80、6g对甲苯磺酸,放入一次性纸杯,迅速搅拌均匀,70℃下发泡固化0.5h,得褐煤基酚醛泡沫,密度为49kg/m3,导热系数为0.038W/(m·K),粉化率为7.0%,粉化率明显低于同条件下制备的纯酚醛泡沫(9.4%),这意味着酚醛泡沫的韧性得到显著增强。
实施例6
称取20g锡林郭勒褐煤,在高压釜中300℃下进行乙醇解反应2h,冷却至室温后,取出反应混合物,过滤,浓缩得乙醇解可溶物,乙醇解可溶物收率为57.4%。取10g褐煤乙醇解可溶物、10g苯酚、0.9gNaOH、6g去离子水,放入三口烧瓶加热至85℃,0.5h后逐滴加入甲醛水溶液31.2g,反应2h后,降至60℃,加乙酸调pH至6,浓缩得到褐煤基树脂,固含量为77%,粘度为3.8Pa·s。取20g树脂、4g正戊烷、0.6g吐温-80、6g对甲苯磺酸,放入一次性纸杯,迅速搅拌均匀,70℃下发泡固化0.5h,得褐煤基酚醛泡沫,密度为40kg/m3,导热系数为0.033W/(m·K),粉化率为6.2%,粉化率明显低于同条件下制备的纯酚醛泡沫(9.6%),这意味着酚醛泡沫的韧性得到显著增强。
Claims (7)
2.如权利要求1所述的褐煤基增韧酚醛泡沫,其特征在于,所述褐煤基树脂的粘度为2-4Pa.s,固含量为70-85%。
3.如权利要求1所述的褐煤基增韧酚醛泡沫,其特征在于,所述表面活性剂为吐温-80。
4.如权利要求1所述的褐煤基增韧酚醛泡沫,其特征在于,所述固化剂为对甲苯磺酸、草酸、磷酸以及盐酸中的一种或两种。
5.如权利要求1所述的褐煤基增韧酚醛泡沫,其特征在于,所述发泡剂为低沸点烷烃类溶剂。
6.如权利要求5所述的褐煤基增韧酚醛泡沫,其特征在于,所述低沸点烷烃类溶剂为正戊烷、正己烷、环己烷以及石油醚30-60中的一种或两种。
7.如权利要求1-6所述的褐煤基增韧酚醛泡沫的制备方法,其特征在于包括如下步骤:
首先将褐煤进行乙醇解,所得可溶物部分替代苯酚与甲醛进行缩聚制备褐煤基树脂,然后取该树脂与表面活性剂、发泡剂、固化剂在室温下充分搅拌混合,在50-90℃下发泡10-90min,得到本发明目标产物:褐煤基增韧酚醛泡沫。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011075926.9A CN112194875A (zh) | 2020-10-10 | 2020-10-10 | 一种褐煤基增韧酚醛泡沫及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011075926.9A CN112194875A (zh) | 2020-10-10 | 2020-10-10 | 一种褐煤基增韧酚醛泡沫及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112194875A true CN112194875A (zh) | 2021-01-08 |
Family
ID=74014232
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011075926.9A Pending CN112194875A (zh) | 2020-10-10 | 2020-10-10 | 一种褐煤基增韧酚醛泡沫及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112194875A (zh) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4595710A (en) * | 1978-09-14 | 1986-06-17 | Company "A" (Foam) Limited | Foamed plastics materials |
CN102898118A (zh) * | 2012-10-25 | 2013-01-30 | 中国地质大学(北京) | 一种粉煤灰增强泡沫炭材料及其制备方法 |
CN103059503A (zh) * | 2013-01-11 | 2013-04-24 | 陕西煤业化工技术研究院有限责任公司 | 一种酚醛泡沫塑料及其制备方法以及泡沫炭的制备方法 |
CN106517138A (zh) * | 2016-11-11 | 2017-03-22 | 中国科学院山西煤炭化学研究所 | 一种无机纳米粒子原位增强树脂基泡沫炭的制备方法 |
CN107602808A (zh) * | 2017-10-11 | 2018-01-19 | 安徽工业大学 | 一种利用褐煤碱解聚产物制备的聚氨酯发泡材料 |
-
2020
- 2020-10-10 CN CN202011075926.9A patent/CN112194875A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4595710A (en) * | 1978-09-14 | 1986-06-17 | Company "A" (Foam) Limited | Foamed plastics materials |
CN102898118A (zh) * | 2012-10-25 | 2013-01-30 | 中国地质大学(北京) | 一种粉煤灰增强泡沫炭材料及其制备方法 |
CN103059503A (zh) * | 2013-01-11 | 2013-04-24 | 陕西煤业化工技术研究院有限责任公司 | 一种酚醛泡沫塑料及其制备方法以及泡沫炭的制备方法 |
CN106517138A (zh) * | 2016-11-11 | 2017-03-22 | 中国科学院山西煤炭化学研究所 | 一种无机纳米粒子原位增强树脂基泡沫炭的制备方法 |
CN107602808A (zh) * | 2017-10-11 | 2018-01-19 | 安徽工业大学 | 一种利用褐煤碱解聚产物制备的聚氨酯发泡材料 |
Non-Patent Citations (4)
Title |
---|
李应平等: ""酚醛泡沫生产及技术研究进展"", 《广东化工》 * |
李应平等: ""酚醛泡沫生产及技术研究进展"", 《广东化工》, vol. 42, no. 7, 31 December 2015 (2015-12-31), pages 33 - 38 * |
袁晓晓等: ""粗酚部分替代苯酚制备酚醛泡沫保温材料"", 《合成树脂及塑料》 * |
袁晓晓等: ""粗酚部分替代苯酚制备酚醛泡沫保温材料"", 《合成树脂及塑料》, vol. 30, no. 3, 31 December 2013 (2013-12-31), pages 109 - 110 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wüst et al. | Understanding the influence of biomass particle size and reaction medium on the formation pathways of hydrochar | |
Li et al. | Lignin as a green and multifunctional alternative to phenol for resin synthesis | |
NL2023946B1 (en) | A Method of Separating Hemicellulose through Efficient Pretreatment of Fibrous Biomass and Comprehensively Utilizing the Same | |
CN102173980B (zh) | 工业木质素热化学转化制备酚类化学品的方法 | |
CN102351564B (zh) | 一种利用煤沥青和生物质原料烧结制备木陶瓷的方法 | |
CN101269930B (zh) | 酶解木质素或它的衍生物改性酚醛发泡材料及其制备方法 | |
WO2018196801A1 (zh) | 高浓度生物质浆料及其制备方法与应用 | |
CN101817692B (zh) | 溶剂型木质素改性树脂制备木陶瓷的方法 | |
CN110156945B (zh) | 一种无甲醛生物质基胶黏剂的制备方法 | |
CN107128914A (zh) | 石油焦基柱状活性炭的制备方法 | |
Xu et al. | Tetrahydro-2-furanmethanol pretreatment of eucalyptus to enhance cellulose enzymatic hydrolysis and to produce high-quality lignin | |
CN101544919B (zh) | 醇基汽油助溶剂及制备方法 | |
CN113247894A (zh) | 一种纸浆-电容炭联合生产的方法 | |
Khandelwal et al. | Conversion of biomass into hydrogen by supercritical water gasification: a review | |
Chen et al. | Comprehensive research on the solid, liquid, and gaseous products of rice husk and rice straw torrefaction | |
CN103193833A (zh) | 生物质加压液化与定向萃取分离制备单糖酯和多酚产物的方法 | |
CN112194875A (zh) | 一种褐煤基增韧酚醛泡沫及其制备方法 | |
CN103483597B (zh) | 一种碱活化改性酶解木质素的方法 | |
Xu et al. | Fates of the components in cotton stalk during the hydrothermal oxidative pretreatment and its relationship with the upgrading of biochar pellets and wood vinegar | |
CN106380887A (zh) | 一种木质素基酚醛模塑料的制备方法 | |
CN104560093A (zh) | 一种生物质制取燃料油的方法 | |
CN103554397A (zh) | 功能化离子液体增强改性酚醛树脂及其制备方法 | |
Bi et al. | Influence of pyrolysis and torrefaction pretreatment temperature on the pyrolysis product distribution | |
CHENG et al. | Preparation and characterization of low-temperature coal tar toughened phenolic foams | |
CN104211889A (zh) | 一种发泡用木质素改性酚醛树脂及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210108 |
|
WD01 | Invention patent application deemed withdrawn after publication |