CN106245235A - 一种熔喷吸油材料 - Google Patents

一种熔喷吸油材料 Download PDF

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CN106245235A
CN106245235A CN201610860174.4A CN201610860174A CN106245235A CN 106245235 A CN106245235 A CN 106245235A CN 201610860174 A CN201610860174 A CN 201610860174A CN 106245235 A CN106245235 A CN 106245235A
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melt
oil
absorption material
oil absorption
polypropylene
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康卫民
何宏升
程博闻
庄旭品
李晓捷
邓南平
刘亚
任元林
赵义侠
李磊
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Tianjin Polytechnic University
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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/14Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
    • D04H3/147Composite yarns or filaments
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005Synthetic yarns or filaments
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

本发明公开了一种熔喷吸油材料,其特征在熔喷纤维体中包括聚苯乙烯和聚丙烯两种热塑性聚合物,所述聚苯乙烯和聚丙烯的质量百分比为:聚丙烯70%~95%,聚苯乙烯5%~30%。本发明的熔喷吸油材料具有纤维直径细、结构蓬松、孔隙率高、密度小的特点,且纤维的结晶度低,极大提升了产品的吸油倍率和吸油速率,本发明的熔喷吸油材料吸油倍率可高达15.8g/g,4min内即可达到吸收饱和。

Description

一种熔喷吸油材料
技术领域
本发明涉及非织造吸油材料,具体为一种熔喷吸油材料,属于环保技术领域。
背景技术
随着能源工业和科学技术的快速发展,工业、餐饮行业和日常生活含油废液等大量的排放,造成了严重的生态环境污染和能源浪费,其中石油类污染对人类以及生存环境的危害最为严重。我国是石油消费大国,消费量已居世界前列。在对石油进行开采、运输、装卸、加工和使用过程中,油轮发生溢油事故和轮船含油污水排放经常发生,严重污染水质,例如2010年4月,美国一座海上钻井平台发生爆炸,引发墨西哥湾原油泄漏事件,约有500万桶原油流入墨西哥湾,污染波及到沿岸5个州,造成了高达千亿美元的经济损失以及大量海洋生物的死亡,给经济和环境带来空前的灾难;其次是地下油罐和输油管线腐蚀渗漏污染土壤和地下水源,不仅造成土壤盐碱化、毒化,导致土壤破坏和废毁,而且其有毒物能通过农作物尤其是地下水进入食物链系统,最终直接危害人类,严重影响了人们的生活和社会的发展。
为更有效地防治和处理油类污染,满足社会经济发展和进步的需求,研究开发各种快速、高效的吸油材料和油品处理技术显得尤为重要。早在上世纪70年代,众多相关研究人员对此技术难题进行了系统全面的探索,并取得了一定的科研成果,熔喷非织造吸油材料开始逐步进入公众的视野,并广泛应用于环保工程、油水分离工程以及海洋石油泄漏等领域,引起了许多国家的广泛关注。近些年来,国内外对熔喷吸油材料开展了大量的研究工作。专利申请号为201610292046.4公布了一种聚苯硫醚熔喷复合纤维吸油无纺布及其制备方法,该发明以聚苯硫醚和聚丙烯为原料,采用熔喷技术和热处理以及热轧等手段得到吸油无纺布。该方法制备的吸油无纺布耐酸碱、强力高、吸油率高,但是持油率、吸附稳定性以及重复利用率等性能并没有得到明显改善。专利申请号为201310655165.8公布了一种共聚甲基丙烯酸酯/聚丙烯复合吸油材料的制备方法,该发明结合了吸油树脂与聚丙烯纤维两种材料的优良特性,通过在聚丙烯非织造布吸油材料基体大分子内部构建高吸油树脂交联网络结构获得复合结构聚丙烯非织造布吸油材料。通过该种方法得到的吸油材料较好地改善了传统熔喷聚丙烯非织造布吸油材料持油率差等缺陷,但是所述吸油材料油水选择性差,而且制备方法较为繁琐,使得加工成本提高。专利申请号为201310416824.2公布了一种具有皮/芯复合结构的吸油毡材料,该发明将丙纶熔喷无纺布材料作为皮层材料,丙纶/涤纶的混合熔喷无纺布材料作为芯层材料,并且采用热压方式形成密闭的包覆结构。通过该方法得到的吸油毡材料能够吸附自重10~15倍的油品,且油品难以泄漏,但是吸油过程难以满足连续、高效等需求。李峰等[李峰,张超,栾国华,等.一种基于高吸油树脂与聚丙烯复合吸油材料[J].河北工业大学学报,2015(1):45-49.]按照一定比例将甲基丙烯酸酯、甲基丙烯酸β羟乙酯、苯乙烯3种单体进行混合,采用悬浮聚合技术制备出共聚甲基丙烯酸酯聚合物高吸油树脂。在此基础上,他们将高吸油树脂和聚丙烯以合适的比例进行复合造粒并采用熔喷工艺成功制备出复合吸油产品,不过该产品吸油量、吸油倍率、保油以及可重复使用性能等还有很大的上升空间,而且聚合改性工艺技术较为复杂,加工成本相对较高。此外,上述几种聚苯硫醚、共聚甲基丙烯酸酯和涤纶的密度相对较大,所制得的熔喷产品密度极易比水的比重大,特别是后两者具有较好的吸水特性,在吸油过程中产品容易沉于水中。
发明内容
本发明所要解决的技术问题是,克服现有技术中的不足,提供一种熔喷吸油材料,特别设计了由两种低密度、高倍差熔融指数的聚丙烯和聚苯乙烯热塑性高聚物进行共混复合制得,该方法制得的熔喷吸油材料具有纤维直径细、结构蓬松、孔径小、孔隙率高、密度小等特点,极大提升了产品的吸油倍率和吸油速率,同时避免了产品沉于水底带来的回收困难。
本发明解决所述的熔喷吸油材料技术问题的技术方案是:设计一种熔喷纤维非织造材料,其特征在于熔喷纤维体中包括两种密度低的聚丙烯和聚苯乙烯热塑性聚合物,所述聚丙烯和聚苯乙烯的质量百分比为:聚丙烯70%~95%,聚苯乙烯5%~30%;所述聚丙烯密度为0.90~0.91g/cm3,所述聚苯乙烯密度为1.04~1.06g/cm3
所述的熔喷纤维非织造材料,其特征在于所述聚丙烯熔融指数范围为1000g/10min~1200g/10min,所述聚苯乙烯熔融指数范围为20g/10min~30g/10min;
所述的熔喷吸油材料,其特征在于所述熔喷纤维的结晶度范围为10%~20%。
本发明所述熔喷吸油材料加工技术是公知熔喷技术,技术成熟,工艺简单,没有使用特殊或专用的设备,易于工业化实施。本发明使用的聚丙烯是熔喷级聚丙烯树脂,具有极高的熔融指数,其熔点为165℃,聚苯乙烯选择的是纺丝级聚苯乙烯树脂,其熔点为240℃,原料易得,无需特殊改性,而且二者均具有良好的疏水能力。本发明的熔喷吸油材料,组方中设计了适量比例密度小、高倍差融指数的聚丙烯和聚苯乙烯共混聚合物,并采用适当的工艺方法而制成。
本发明熔喷吸油材料技术设计原理在于三方面,一是选择两种密度小的聚合物共混,在本发明配方比例下,所制得的熔喷纤维密度不高于0.96g/cm3,低于水的密度,能够较好地适用于海上漏油吸附回收;二是高倍差熔融指数使得二者在熔喷加工过程中出现流动性差异而在共混纤维体中形成一定的微相界面分离,该微相分离界面存在有助于降低纤维密度和提供油储空穴,提高产品的吸油能力;三是高倍差熔融指数聚合物共混熔喷纤维的结晶度更低,无定型区的大分子更有助于油分子向纤维体中渗透,提高其吸附速率。与纯聚丙烯熔喷吸油材料相比,本发明的熔喷吸油材料具有纤维直径细、结构蓬松、孔隙率高、密度小的特点,且纤维的结晶度低,极大提升了产品的吸油倍率和吸油速率,本发明的熔喷吸油材料结晶度为10%,吸油倍率可高达15.8g/g,4min内即可达到吸收饱和,保油率为98.3%。
附图说明
图1为本发明实施例5所述一种熔喷吸油材料的电镜扫描示意图。
具体实施方式
下面结合具体实施例对本发明做进一步详细描述。
实施例1
将密度为0.90g/cm3、熔融指数为1000g/10min、质量百分比95%的聚丙烯与密度为1.04g/cm3、熔融指数为20g/10min、质量百分比5%的聚苯乙烯放入高速搅拌器中高速搅拌混合均匀后,加入到螺杆挤出机中熔融挤出,再经料路、计量泵,进入熔喷模头,熔体在熔喷模头出口处与高速热空气相遇,并在高速热空气作用下牵伸细化,然后沉积于收网帘上形成聚苯乙烯/聚丙烯共混熔喷吸油材料。经测试,该吸油材料结晶度为20%,吸油倍率达到8.6g/g,6min内即可达到吸收饱和,保油率为85.5%。
实施例2
将密度为0.90g/cm3、熔融指数为1100g/10min、质量百分比90%的聚丙烯与密度为1.05g/cm3、熔融指数为25g/10min、质量百分比10%的聚苯乙烯放入高速搅拌器中高速搅拌混合均匀后,加入到螺杆挤出机中熔融挤出,再经料路、计量泵,进入熔喷模头,熔体在熔喷模头出口处与高速热空气相遇,并在高速热空气作用下牵伸细化,然后沉积于收网帘上形成聚苯乙烯/聚丙烯共混熔喷吸油材料。经测试,该吸油材料结晶度为18%,吸油倍率达到9.4g/g,6min内即可达到吸收饱和,保油率为87.8%。
实施例3
将密度为0.91g/cm3、熔融指数为1100g/10min、质量百分比85%的聚丙烯与密度为1.06g/cm3、熔融指数为25g/10min、质量百分比15%的聚苯乙烯放入高速搅拌器中高速搅拌混合均匀后,加入到螺杆挤出机中熔融挤出,再经料路、计量泵,进入熔喷模头,熔体在熔喷模头出口处与高速热空气相遇,并在高速热空气作用下牵伸细化,然后沉积于收网帘上形成聚苯乙烯/聚丙烯共混熔喷吸油材料。经测试,该吸油材料结晶度为17%,吸油倍率达到11.3g/g,5min内即可达到吸收饱和,保油率为92.6%。
实施例4
将密度为0.91g/cm3、熔融指数为1200g/10min、质量百分比80%的聚丙烯与密度为1.06g/cm3、熔融指数为30g/10min、质量百分比20%的聚苯乙烯放入高速搅拌器中高速搅拌混合均匀后,加入到螺杆挤出机中熔融挤出,再经料路、计量泵,进入熔喷模头,熔体在熔喷模头出口处与高速热空气相遇,并在高速热空气作用下牵伸细化,然后沉积于收网帘上形成聚苯乙烯/聚丙烯共混熔喷吸油材料。经测试,该吸油材料结晶度为14%,吸油倍率达到13.5g/g,5min内即可达到吸收饱和,保油率为95.7%。
实施例5
将密度为0.91g/cm3、熔融指数为1100g/10min、质量百分比75%的聚丙烯与密度为1.05g/cm3、熔融指数为30g/10min、质量百分比25%的聚苯乙烯放入高速搅拌器中高速搅拌混合均匀后,加入到螺杆挤出机中熔融挤出,再经料路、计量泵,进入熔喷模头,熔体在熔喷模头出口处与高速热空气相遇,并在高速热空气作用下牵伸细化,然后沉积于收网帘上形成聚苯乙烯/聚丙烯共混熔喷吸油材料。经测试,该吸油材料结晶度为10%,吸油倍率达到15.8g/g,4min内即可达到吸收饱和,保油率为98.3%。
实施例6
将密度为0.91g/cm3、熔融指数为1100g/10min、质量百分比70%的聚丙烯与密度为1.05g/cm3、熔融指数为30g/10min、质量百分比30%的聚苯乙烯放入高速搅拌器中高速搅拌混合均匀后,加入到螺杆挤出机中熔融挤出,再经料路、计量泵,进入熔喷模头,熔体在熔喷模头出口处与高速热空气相遇,并在高速热空气作用下牵伸细化,然后沉积于收网帘上形成聚苯乙烯/聚丙烯共混熔喷吸油材料。经测试,该吸油材料结晶度为13%,吸油倍率达到14.6g/g,5min内即可达到吸收饱和,保油率为97.2%。
实施例7
将密度为0.91g/cm3、熔融指数为1100g/10min的聚丙烯加入到螺杆挤出机中熔融挤出,再经料路、计量泵,进入熔喷模头,熔体在熔喷模头出口处与高速热空气相遇,并在高速热空气作用下牵伸细化,然后沉积于收网帘上形成聚丙烯熔喷吸油材料。经测试,该吸油材料结晶度为20%,吸油倍率为7.8g/g,8min达到吸收饱和,保油率为83.7%。

Claims (3)

1.一种熔喷吸油材料,其特征在于熔喷纤维体中包括两种密度小的聚丙烯和聚苯乙烯热塑性聚合物,所述聚丙烯和聚苯乙烯的质量百分比为:聚丙烯70%~95%,聚苯乙烯5%~30%;所述聚丙烯密度为0.90~0.91g/cm3,所述聚苯乙烯密度为1.04~1.06g/cm3
2.根据权利要求1所述一种熔喷吸油材料,其特征在于所述聚丙烯熔融指数范围为1000g/10min~1200g/10min,所述聚苯乙烯熔融指数范围为20g/10min~30g/10min。
3.根据权利要求1或2所述的熔喷吸油材料,其特征在于熔喷纤维的结晶度范围为10%~20%。
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