CN113024743B - 一种双组份生物转盘用pvdc乳胶 - Google Patents
一种双组份生物转盘用pvdc乳胶 Download PDFInfo
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- CN113024743B CN113024743B CN202110249284.8A CN202110249284A CN113024743B CN 113024743 B CN113024743 B CN 113024743B CN 202110249284 A CN202110249284 A CN 202110249284A CN 113024743 B CN113024743 B CN 113024743B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/08—Aerobic processes using moving contact bodies
- C02F3/082—Rotating biological contactors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- D—TEXTILES; PAPER
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- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
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- Environmental & Geological Engineering (AREA)
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Abstract
本发明涉及一种双组份生物转盘用PVDC乳胶,A组分包括以下重量份的原料:30‑40份偏二氯乙烯、4‑7份甲氧基聚乙二醇(甲基)丙烯酸酯、3‑5份(甲基)丙烯酸烷基酯,2‑4份(甲基)丙烯酸缩水甘油醚、0.1‑0.3份乳化剂、0.05‑0.1份引发剂;B组分包括如下质量份的原料:30‑40份偏二氯乙烯、4‑7份甲氧基聚乙二醇(甲基)丙烯酸酯、3‑5份(甲基)丙烯酸烷基酯、3‑5份不饱和羧酸、0.1‑0.3份乳化剂、0.05‑0.1份引发剂。本发明的双组份PVDC乳胶,使用时按照一定质量配比将A组分和B组分喷涂于PVDC树脂形成的立体网状结构,经过热压定形得到的生物转盘盘片材料结构稳固,力学强度好,挂膜量高;相对于非专用于PVDC生物转盘的乳胶,本发明的双组份PVDC乳胶在很小用量下就能保证生物转盘盘片强度。
Description
技术领域
本发明属于高分子合成领域,具体涉及一种双组份生物转盘用PVDC乳胶。
背景技术
生物转盘技术是一种生物膜法污水处理技术,具有设计灵活,安装便捷,操作简单,运行费用低,不需要曝气,节约能源,在较短的生物接触时间内即可得到较高的净化效果。生物转盘组件是多张盘片间隔后安装在旋转轴上,各个盘片部分浸渍在污水中,污水与附着在盘片上的需氧菌接触进行生物处理。
生物转盘的盘片是主要组成部分,也是影响废水处理效果的关键因素。盘片的性能具有很重要的意义。要生物转盘具有高的处理效率,就需要盘片具有以下性能:1,比表面积大,挂膜性能好,携带微生物生物量大;2,力学强度高,长期运行不会发生形变;3,阻隔性好,由于生物转盘是长期处于水中工作,要求疏水性好,长久浸泡不会瓦解,变形;4,抗腐蚀性能好,由于不同来源的废水,具有不同的酸碱度,盐度,要求生物转盘能够耐腐蚀,在酸或碱,或高盐度的环境下耐腐蚀;5,生物膜着床率高,生物膜不易脱落。
日本旭化成公司研发了一类PVDC材料,加工成立体网状材料,孔隙率95-98%的丝网状态,生物层可以进入立体网格状的内部,可以避免盘片表面生物层的脱落。尽管原因还未明,但PVDC相比常规的塑料材质,比如聚烯烃,聚氨酯类的材料有更好的生物附着量,是目前生物转盘的最具前景的材料。在制备基于PVDC的膜丝后,还需要用乳胶将交叠铺网的膜丝粘结起来,热定形后剪裁为需要的形状即得到生物转盘的盘片材料。出于材料一致性的考虑,现有的PVDC盘片都使用PVDC乳胶,制备时是将PVDC材料造粒、拉丝、成网后,喷涂PVDC乳胶,热定型制得孔隙率90%以上的材料。采用的PVDC乳胶一般为市面上常见的商购的PVDC乳胶,并不是专门为生物转盘的粘合制造的乳胶。虽然也能起到粘合作用,但是存在用量大,而且一般商购的PVDC乳胶一般是作为涂料涂层材料使用,往往具有很高的阻隔性,但是这种阻隔性并不利于微生物膜在生物转盘表面的形成,即不利于挂膜。因此,开发一类生物转盘专用的PVDC乳胶具有重要的意义。
发明内容
为克服现有技术中生物转盘用PVDC乳胶用量大,所得生物转盘挂膜量低的缺陷,本发明提供了一种生物转盘用PVDC乳胶,其是由偏二氯乙烯、甲氧基聚乙二醇(甲基)丙烯酸酯、聚乙烯醇缩醛共聚得到,所得PVDC乳胶稳定、固含量高,用于生物转盘膜丝粘结用量少,所得生物转盘对微生物亲和性好,挂膜量高,此类PVDC乳胶之前未见报道。
本发明的第一个目的是提供一种双组份生物转盘用PVDC乳胶,A组分包括以下重量份的原料:30-40份偏二氯乙烯、4-7份甲氧基聚乙二醇(甲基)丙烯酸酯、3-5份(甲基)丙烯酸烷基酯,2-4份(甲基)丙烯酸缩水甘油醚、0.1-0.3份乳化剂、0.05-0.1份引发剂;B组分包括如下质量份的原料:30-40份偏二氯乙烯、4-7份甲氧基聚乙二醇(甲基)丙烯酸酯、3-5份(甲基)丙烯酸烷基酯、3-5份不饱和羧酸、0.1-0.3份乳化剂、0.05-0.1份引发剂。
进一步地,所述甲氧基聚乙二醇(甲基)丙烯酸酯选自甲氧基聚乙二醇丙烯酸酯和甲氧基聚乙二醇甲基丙烯酸酯中的至少一种;所述(甲基)丙烯酸烷基酯选自(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯中的至少一种;所述不饱和羧酸选自(甲基)丙烯酸、顺丁烯二酸中的至少一种。
所述甲氧基聚乙二醇(甲基)丙烯酸酯的分子量为1000-3000g/mol。
所述乳化剂为阴离子表面活性剂和/或非离子型表面活性剂,所述阴离子表面活性剂选自十二烷基硫酸钠(SLS)、十二烷基磺酸钠(SDS),十二烷基苯磺酸钠(SDBS)、仲烷基磺酸钠(SAS)中的至少一种;所述非离子型表面活性剂选自壬基酚聚氧乙烯基醚、聚氧乙烯基辛基酚醚(OP)中的至少一种。优选为SAS和OP-10按照质量比1-2:1-2的复配乳化剂。
所述引发剂没有特别的限定,本发明采用水溶性引发体系,比如过硫酸钾/亚硫酸氢钠的氧化还原引发体系。过硫酸钾和亚硫酸氢钠质量比为1-2:1。
在本发明一个优选技术方案中,所述(甲基)丙烯酸烷基酯为甲基丙烯酸甲基和甲基丙烯酸丁酯按照质量比1-2:1-2的复配,所述不饱和羧酸为丙烯酸和顺丁烯二酸按照质量比3-5:1的复配。
发明人发现,当(甲基)丙烯酸烷基酯为上述复配时,乳液能够取得更好的稳定性;当不饱和羧酸为上述复配时,双组份乳胶喷涂于PVDC纤维丝形成的立体网状结构后,所得材料的力学强度更优。
本发明乳液的单体中,甲氧基聚乙二醇(甲基)丙烯酸酯本身具有一定的表面活性剂的作用,在进行乳液聚合时,可以减少乳化剂的加入量,在PVDC乳胶的制备中,如果乳化剂用量较多,留在乳液内乳化剂,特别是阴离子乳化剂会影响生物转盘的成膜性和耐水性。
优选地,本发明所述双组份生物转盘用PVDC乳胶的A组分和B组分,是混合单体、乳化剂、引发剂通过种子乳液聚合的方法制备得到。
所述种子乳液聚合的方法为本领域所熟知,在本发明一个具体实施方式中,A组分和B组分通过种子乳液聚合的方法包括如下步骤:
(1)将6-10wt%引发剂,2-5wt%的混合单体和水分散,升温至50-60℃,反应2-4h,得到种子乳液;
(2)向步骤(1)所得种子乳液中缓慢加入乳化剂、剩余的混合单体和引发剂,继续升温至60-70℃,反应3-5h,冷却,出料即得A组分/B组分的乳液。
在步骤(1)的种子乳液聚合中,不需要加入乳化剂,因为单体甲氧基聚乙二醇(甲基)丙烯酸酯是一种反应型乳化剂,足够种子粒子的保护和稳定的需求,如果还外加乳化剂,会形成新的胶束或新的乳胶微粒,不利于步骤(2)乳液聚合得到乳胶粒径均一的乳液。
优选地,步骤(1)的升温是升温至50-60℃,步骤(S2)继续升温是升温至60-70℃,冷却是冷却至室温;步骤(2)所述缓慢加入,是剩余料液在2-3h内加入完毕。加入方式为本领域所熟知,比如滴加、或者用计量泵加入。可以事先配制为分散液一起加入,也可以分别加入,没有特别的限定。
本发明还提供了上述双组份生物转盘用PVDC乳胶在制备基于PVDC的生物转盘的用途。
本发明所得双组份PVDC乳胶在使用时,A组分和B组分的比例按照质量比1-1.5:1-1.5配制,喷涂在基于PVDC纤维丝构成的立体网状结构上,再热定型得到生物转盘盘片材料。双组份PVDC乳胶的用量是PVDC树脂质量的40-60%。
所述基于纤维丝构成的立体网状结构可以参考专利CN202246233U,CN103332780A,或者申请人在前的专利CN2021101769764中记载的由PVDC树脂材料经过造粒、拉丝、收卷、铺网得到的立体网状结构。
具体而言,所述立体网状结构是PVDC树脂和辅料共混后,在160-170℃下造粒,经过拉丝得到丝径为1-1.5mm的纤维丝,收卷后通过卷取机定形为卷曲绳,开解得到卷曲纤维,再经过铺网机铺网后得到立体网状结构。
所述辅料选自增塑剂、增韧剂、碳素、二氧化钛、气象白炭黑、脱模剂和抗氧剂中的至少一种。上述辅料的种类和用量为本领域所熟知。比如,所述增塑剂选自邻酞酸二辛酯,用量为PVDC树脂的4-7%;所述增韧剂为高分子增韧剂,具体选自甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物(MBS)、乙烯-醋酸乙烯共聚物(EVA)、乙烯-丙烯酸甲酯共聚物(EMA),乙烯-丙烯共聚物(EAA)、丙烯酸酯共聚弹性体(ACR)中的至少一种,用量为PVDC树脂的2-5%;碳素的粒径为1-5mm,用量为PVDC树脂的0.1-0.3%;二氧化钛的粒径为5-20μm,用量为PVDC树脂的0.5-1%;气象白炭黑的比表面积BET为170-230m2/g,用量为PVDC树脂的0.5-1%;所述脱模剂选自聚二甲基硅氧烷,用量为PVDC树脂的1-3%;所述抗氧剂选自2,6-对二叔丁基对甲酚,用量为PVDC树脂的0.5-1%。
进一步地,所述热定型的温度是120-150℃,在20-30MPa的压力下进行热压得到,可以在热压定形机上完成。压力不宜过大,否则过于致密,孔隙率低,导致挂膜量低。压力以所得PVDC生物转盘的比重为0.07-0.10g/cm3为宜。
进一步地,铺网的层数厚度,以热压后所得PVDC生物转盘盘片材料的厚度为4-7cm为宜。
本发明还提供了一种基于PVDC的生物转盘盘片材料,包括PVDC树脂和上述双组份PVDC乳胶,双组份PVDC乳胶的质量是PVDC树脂的40-60%,所述双组份PVDC乳胶中,A组分和B组分的质量比为1-1.5:1-1.5,优选为1-1.1:1-1.1。
本发明制备得到了PVDC生物转盘专用的乳胶,使得乳胶的用量大为减少,一般PVDC生物转盘盘片材料制备时,所用乳胶量比较大,才能保证所得生物转盘盘片材料的力学强度。本发明制备的双组份PVDC乳胶,成分主要为PVDC,和生物转盘的立体网状结构材质基本一致,使所得生物转盘材料均匀一致,不会影响废水处理时的挂膜量。此外,所得PVDC乳液稳定性好,方便贮藏,60天之内均可以使用而不会影响性能。
优选地,在热定形后,静置5-15天,优选静置8-10天以完成PVDC的结晶后,再进行剪裁。
本发明提供的生物转盘盘片的形状没有特别的限定,一般为圆形,也可以制作为一定角度的扇形,角度为60-90°。比如申请人在前的专利CN201710388394.6记载的,为一个扇形主体。可以在圆形或在扇形主体上可以开设有多个贯穿孔,比如在60°的扇形上开设5-10个贯穿孔,具体比如每个扇形上具有5,6,7,8,9,10个贯穿孔。
相对于现有技术,本发明取得了以下有益效果:
一、本发明制备得到了专用于PVDC生物转盘的双组份PVDC乳胶,使用时按照一定质量配比将A组分和B组分喷涂于PVDC树脂形成的立体网状结构,经过热压定形得到的生物转盘盘片材料结构稳固,力学强度好,挂膜量高。
二、本发明所得双组份PVDC乳胶用于PVDC树脂材料拉丝成网后的立体网状结构的粘结,相对于非专用于PVDC生物转盘的乳胶,用量大为减少就能保证盘片强度,一方面降低了成本,另一方面也降低了乳胶对于生物转盘材料用于废水处理的影响。
附图说明
图1为本发明生物转盘盘片组装后的侧视图。
图2为本发明生物转盘盘片组装后的正视图。
具体实施方式
若无特别说明,本发明试剂和仪器均为可以商购的常规商品。本发明实施例中所述“份”均为质量份,所述“%”均为质量百分比。
PVDC树脂采购自日本旭化成,其原料单体中,偏二氯乙烯/氯乙烯的比例为95:5,分子量为6.2万,熔融温度148.3℃。碳素采购自成都海城远创科技有限公司,灰份≤1%,硫份≤0.5%,平均粒度1.3mm;二氧化钛采购自济南裕兴,型号R818,金红石含量≥98%,粒径约10μm;气象白炭黑采购自瓦克,BET比表面积为180m2/g。甲氧基聚乙二醇丙烯酸酯采购自广州市碳水科技有限公司,分子量约1500。脱模剂聚二甲基硅氧烷采购自吉鹏硅氟材料有限公司,黏度1000CS。C803乳液采购自日本旭化成,固含量约43.6%。
乳液固含量的测试参照GB1725-1979进行测试。
具体是准确称取2g±0.1g乳液于很重的表面皿,加入1滴阻聚剂,在真空烘箱中,在50℃下彻底干燥质量不再变化,采用干物减重法,按照下式计算乳液固含量:
固含量(%)=M2-M0/M1-M0×100%,
式中,M0为表面皿重量(g),M1为表面皿加乳液的质量(g),M2为干燥后表面皿加干胶的质量(g)。
制备例双份组PVDC乳胶的制备
制备例1
A组分的制备:
A组分原料如下:40份偏二氯乙烯、4份甲氧基聚乙二醇丙烯酸酯、4份甲基丙烯酸甲酯,4份甲基丙烯酸缩水甘油醚、50份去离子水、0.1份SAS和0.1份OP-1的复配作为乳化剂,0.04份过硫酸钾和0.02份亚硫酸氢钠的复配作为引发剂。
(A1)将10wt%引发剂,5wt%的混合单体和水分散,升温至50℃,在300rpm的转速下反应2h,得到种子乳液;
(A2)向步骤(A1)所得种子乳液中缓慢加入乳化剂、剩余的混合单体和引发剂,2h加入完毕,继续升温至65℃,反应3h,冷却,出料即得A组分乳液,固含量51.3%;
B组分的制备:
B组分原料如下:40份偏二氯乙烯、4份甲氧基聚乙二醇丙烯酸酯、4份甲基丙烯酸甲酯,4份丙烯酸、50份去离子水、0.1份SAS和0.1份OP-1的复配作为乳化剂,0.04份过硫酸钾和0.02份亚硫酸氢钠的复配作为引发剂。
(B1)将10wt%引发剂,5wt%的混合单体和水分散,升温至50℃,在300rpm的转速下反应2h,得到种子乳液;
(B2)向步骤(B1)所得种子乳液中缓慢加入乳化剂、剩余的混合单体和引发剂,2h加入完毕,继续升温至65℃,反应3h,冷却,出料即得B组分乳液,固含量50.4%。
制备例2
其他条件和步骤和制备例1相同,区别在于A组分和B组分中的4份甲基丙烯酸甲酯均替换为2份甲基丙烯酸甲酯和2份甲基丙烯酸丁酯的复配。A组分乳液固含量51.0%,B组分乳液固含量49.7%。
制备例3
其他条件和步骤和制备例1相同,区别在于B组分中的4份丙烯酸替换为3份丙烯酸和1份顺丁烯二酸的复配。A组分乳液固含量51.2%,B组分乳液固含量49.6%。
制备例4
其他条件和步骤和制备例1相同,区别在于A组分和B组分中的4份甲基丙烯酸甲酯均替换为2份甲基丙烯酸甲酯和2份甲基丙烯酸丁酯的复配,B组分中的4份丙烯酸替换为3份丙烯酸和1份顺丁烯二酸的复配。A组分乳液固含量51.6%,B组分乳液固含量50.1%。
制备例5
其他条件和步骤和制备例4相同,区别在于A组分和B组分中甲氧基聚乙二醇丙烯酸酯的用量改为7份。A组分乳液固含量51.3%,B组分乳液固含量50.8%。
制备例6
其他条件和步骤和制备例1相同,区别在于A组分中乳化剂为0.2份OP-10,组分B中乳化剂为0.2份SAS。A组分乳液固含量50.8%,B组分乳液固含量50.3%。
应用例1
将制备例的双组份乳胶,进行放置稳定性,化学稳定性的测试。其中化学稳定性是取1mL乳液用50mL水稀释,分别用10%氯化钙和缓慢滴定,观察乳液凝聚析出时所消耗的试剂体积。结果如下表1所示:
表1
我们注意到,制备例5和制备例4的乳液比较,制备例5所用乳化剂用量增加,乳液稳定性有所增强,但是乳化剂用量增大的情况下,乳液中乳胶微粒过细,化学稳定性和耐水性下降。通过制备例6可以看出,对于本发明制备得到的PVDC乳胶,无论是A组分还是B组分,采用SAS和OP-10复配的乳化剂对于乳液的稳定性能最好。
实施例生物转盘盘片的制备
实施例1
按照以下步骤加工制备生物转盘盘片。
(1)混料:将100份PVDC树脂,6份邻酞酸二辛酯,3.5份EAA,0.2份碳素,0.7份二氧化钛,0.6份气象白炭黑,1.5份聚二甲基硅氧烷,0.5份2,6-对二叔丁基对甲酚,一起在高混机中加热至80℃混合,混合后原料进入冷混机降温混合完成混料;
(2)造粒:将步骤(1)所得混料加入双螺杆挤出机,在150-160℃的工作温度下挤出造粒,冷却定型,切粒得到PVDC母粒;
(3)拉丝,收卷:将步骤(2)所得PVDC母粒烘干,进入单螺杆拉丝挤出机,工作维度140-150℃,挤出,初步冷却成型的PVDC塑料丝通过五棍牵引机进行初步拉伸定型,定型完的塑料丝进入延伸水槽再次加热,加热后的塑料丝通过七棍牵引机进行最终拉伸定型,拉伸比5:1,丝径为1.2mm,通过收卷机进行收卷;
(4)铺网,热压,定形:将步骤(3)收卷后的PVDC塑料丝通过三维纤维卷曲机进行卷曲定型形成卷曲绳,裁断机裁断成30cm的绳段,通过卷曲纤维解除机解开卷曲绳,得到卷曲径25mm的三维卷曲纤维,通过铺网机进行称重,并铺网成立体网状结构的纤维丝,按照A组分和B组分的质量比1:1将制备例1的双组份PVDC乳胶均匀喷涂于上述立体网络结构的纤维丝上,双组份PVDC乳胶的总用量为立体网状结构的纤维丝质量的60%,热压机定形,热压机温度为130℃,压力20MPa,制得厚度为5cm,孔隙率96%的板材,静置8天。
实施例2-6
其他条件和步骤和实施例1相同,区别在于步骤(4)中,双组份PVDC乳胶分别为制备例2-6制得。
实施例7
其他条件和步骤和实施例1相同,区别在于步骤(4)中,双组份PVDC乳胶的总用量为立体网状结构的纤维丝质量的40%
对比例1
其他条件和步骤和实施例1相同,区别在于步骤(4)中,双组份PVDC乳胶替换为日本旭化成公司生产的C803乳胶(其主要成分是PVDC),由于C803乳胶和制备例1的双组份乳胶固含量不同,为保持乳胶有效成分相同用量的情况下比较,对比例1中C803乳胶用量为立体网状结构的纤维丝质量的70%,这样折算为固含量后,对比例1和实施例1乳胶有效成分用量接近。
对比例2
其他条件和步骤和对比例1相同,区别在于步骤(4)中,C803乳胶的用量为立体网状结构的纤维丝质量的110%。
应用例1
测试上述实施例和对比例的板材的各项数据,每次测试5个样本(n=5),取平均值,结果如下表2所示:
拉伸强度的测试参照GB/T1040.4-2006进行。
表2
由于在生物转盘运行过程中,随着生物膜越在盘片表面附着越来越多,形成越来越厚的生物膜,拉伸强度可以表示生物转盘承受重量的能力,拉伸强度越大,纤维变形量越小,说明生物转盘盘片抗变形的能力越强,稳定性越好,使用寿命越久。本发明制备的生物转盘盘片可以连续工作10年以上。通过表2数据可知,本发明提供的双组份PVDC乳胶,用于PVDC生物转盘制备时PVDC树脂制成的纤维丝的立体网状结构的粘合粘结时,可以在更小的乳胶用量下,就能达到普通PVDC乳胶接近的拉伸强度。这样,有利于生物转盘在废水处理时具有更高的挂膜量。
应用例2
将上述实施例和对比例的板材剪裁为半径1m,角度60°的扇形,并在每个扇形均匀分散开设6个贯穿孔,每个贯穿孔直径为4.2cm,6个扇形组成一个半径1m的圆形,安装在镂空的骨架上,如图1和图2所示。
生物转盘主要工作参数如下:盘片30个,盘片直径1m,转盘转速4r/min,连续运行进行污水处理,污水来自城镇污水厂进水,处理水量3000m3/d,水质:COD=420mg/L,BOD=160mg/L,氨氮=62mg/L,总氮=85mg/L,总磷=11mg/L,SS=250mg/L。将生物转盘放置在缺氧区内,DO=0.1-0.3mg/L,在生化池接种活性污泥浓度2800mg/L,芽孢杆菌浓度800mg/L,期间24小时连续进水,不再补充活性污泥和芽孢杆菌,生化池污泥浓度维持在3500mg/L-4500mg/L,好氧DO值维持在0.8-1mg/L。连续运行30天从盘片上取下生物膜,在烘箱中恒重后测定其质量,计算得到单位面积盘片上的生物膜质量为挂膜量。还测试了单位面积的生物盘片每天能够处理的BOD的量,结果如下表3所示。
表3
Claims (10)
1.一种双组份生物转盘用PVDC乳胶,A组分包括以下重量份的原料:30-40份偏二氯乙烯、4-7份甲氧基聚乙二醇(甲基)丙烯酸酯、3-5份(甲基)丙烯酸烷基酯,2-4份(甲基)丙烯酸缩水甘油醚、0.1-0.3份乳化剂、0.05-0.1份引发剂;B组分包括如下质量份的原料:30-40份偏二氯乙烯、4-7份甲氧基聚乙二醇(甲基)丙烯酸酯、3-5份(甲基)丙烯酸烷基酯、3-5份不饱和羧酸、0.1-0.3份乳化剂、0.05-0.1份引发剂;
所述(甲基)丙烯酸烷基酯为甲基丙烯酸甲酯和甲基丙烯酸丁酯按照质量比1-2:1-2的复配;和/或所述不饱和羧酸为丙烯酸和顺丁烯二酸按照质量比3-5:1的复配。
2.如权利要求1所述的PVDC乳胶,其特征在于,所述甲氧基聚乙二醇(甲基)丙烯酸酯的分子量为1000-3000g/mol。
3.如权利要求1所述的PVDC乳胶,其特征在于,所述乳化剂为阴离子表面活性剂和/或非离子型表面活性剂,所述阴离子表面活性剂选自十二烷基硫酸钠、十二烷基磺酸钠,十二烷基苯磺酸钠、仲烷基磺酸钠中的至少一种;所述非离子型表面活性剂选自壬基酚聚氧乙烯基醚、聚氧乙烯基辛基酚醚中的至少一种。
4.如权利要求3所述的PVDC乳胶,其特征在于,所述乳化剂为仲烷基磺酸钠和聚氧乙烯基辛基酚醚按照质量比1-2:1-2的复配乳化剂。
5.如权利要求1所述的PVDC乳胶,其特征在于,所述A组分和B组分,是混合单体、乳化剂、引发剂通过种子乳液聚合的方法制备得到。
6.如权利要求5所述的PVDC乳胶,其特征在于,所述种子乳液聚合的方法,包括如下步骤:
(1)将6-10wt%引发剂,2-5wt%的混合单体和水分散,升温至50-60℃,反应2-4h,得到种子乳液;
(2)向步骤(1)所得种子乳液中缓慢加入乳化剂、剩余的混合单体和引发剂,继续升温至60-70℃,反应3-5h,冷却,出料即得A组分/B组分的乳液。
7.权利要求1-6任一项所述双组份生物转盘用PVDC乳胶在制备基于PVDC的生物转盘的用途。
8.如权利要求7所述的用途,其特征在于,所述双组份PVDC乳胶在使用时,A组分和B组分的比例按照质量比1-1.5:1-1.5配制,喷涂在基于PVDC纤维丝构成的立体网状结构上,再热定型得到生物转盘盘片材料;双组份PVDC乳胶的用量是PVDC树脂质量的40-60%。
9.如权利要求7所述的用途,其特征在于,所述立体网状结构是PVDC树脂和辅料共混后,在160-170℃下造粒,经过拉丝得到丝径为1-1.5mm的纤维丝,收卷后通过卷取机定形为卷曲绳,开解得到卷曲纤维,再经过铺网机铺网后得到立体网状结构;
所述辅料选自增塑剂、增韧剂、碳素、二氧化钛、气相白炭黑、脱模剂和抗氧剂中的至少一种。
10.一种基于PVDC的生物转盘盘片材料,其特征在于,由PVDC的立体网状结构和权利要求1-6任一项所述的双组份PVDC乳胶经过热压定形而成,所述双组份PVDC乳胶的质量是PVDC的立体网状结构的40-60%,所述PVDC的立体网状结构是PVDC树脂和辅料一起经过混料、造粒、拉丝、铺网得到。
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