CN110183553B - 一种亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络及其应用 - Google Patents
一种亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络及其应用 Download PDFInfo
- Publication number
- CN110183553B CN110183553B CN201910470421.3A CN201910470421A CN110183553B CN 110183553 B CN110183553 B CN 110183553B CN 201910470421 A CN201910470421 A CN 201910470421A CN 110183553 B CN110183553 B CN 110183553B
- Authority
- CN
- China
- Prior art keywords
- polystyrene
- hydrophilic
- interpenetrating polymer
- polymer network
- polyacrylamide
- 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.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络及其应用。所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络的粒径分布为0.25~0.85mm,平均孔径为8~40nm,活性氨基含量0.6~2.2mmol/g,平均比表面积为150~1000m2/g,总孔容为0.5~1.3cm3/g。本发明通过制备聚丙烯酰胺与聚苯乙烯类互穿聚合物网络,引入了亲水性酰胺基团和疏水性官能团,对秸秆水解液进行脱毒处理,能够与水解液中的亲水性发酵抑制物形成分子间氢键,去除大部分的亲水性发酵抑制物,减少了秸秆稀酸水解副产物的含量。
Description
技术领域
本发明涉及功能高分子材料技术领域,具体涉及一种亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络及其应用。
背景技术
化石能源不可再生。大量使用化石能源引起了能源短缺,并带来了严重的环境污染问题。世界各国都加快了对新能源和可再生能源的开发和利用,其中木质纤维素类生物质资源因来源广、数量大、可再生等突出优点而引起了全世界的广泛关注。我国是传统的农业大国,每年产生秸秆类废弃物约9亿吨。传统处理秸秆的方式是焚烧,不仅利用效率低下,而且存在烟尘大,污染环境严重等突出问题。将秸秆类木质纤维素通过生物化学转化方法发酵制备乙醇、丁醇、微生物油脂等生物燃料和生物基化学品,具有广阔的应用前景。在该生化转化工艺中,秸秆水解是重要的一环。其中,稀酸水解反应速率较快,成本相对较低,因而易于产业化应用。通常,秸秆由纤维素、半纤维素和木质素组成。纤维素是葡萄糖单体连接形成的一类直链多糖化合物;半纤维素是通过糖苷键将不同五碳糖(阿拉伯糖和木糖等)和六碳糖(葡糖糖和半乳糖等)连接形成的一类支链多糖化合物;而木质素主要是酚类结构单元构成的高分子化合物。经稀酸水解获得的水解产物复杂,存在许多发酵抑制物,主要包括甲酸、乙酸、乙酰丙酸等有机酸类物质,及5-羟甲基糠醛、糠醛等醛类物质,以及酸溶木质素和色素等。这些副产物对后续的微生物发酵具有强烈的抑制作用。因此,要经过脱毒步骤才能得到可被微生物利用的水解液。
目前水解液脱毒精制的方法主要有生物法、化学法和物理法三种。生物法主要缺点是处理时间长、效率低;化学法对酚类物质去除效果不佳。物理法主要包括蒸馏法、溶剂萃取法及吸附法。其中,物理吸附法因脱毒条件温和、效率高而成为了研究热点。常用的吸附剂主要有活性炭、离子交换树脂和吸附树脂吸附等。活性炭选择性较差,糖损失率较高,且活性炭较难重复使用。离子交换树脂洗脱再生会产生大量的酸碱废水,污染环境。大孔吸附树脂具有机械性能好、孔结构可控、选择性好、容易再生等优点,可望成为秸秆水解液高效脱毒精制的理想介质。但由于其具有较强的疏水性,导致对木质纤维素水解液中亲水性抑制物吸附性能较差,亟待解决该问题,实现对木质纤维素生物质资源的高效利用。
发明内容
本发明提出一种亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络及其应用,采用亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络对木质纤维素水解液进行脱毒,可以有效去除水解液中存在的有机酸类、酚类物质及酸溶木质素等,且吸附剂容易再生、成本低廉,克服了传统脱毒技术的显著缺陷,为木质纤维素水解液脱毒提供了一个新的技术途径。
本发明的目的是提出了一种亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络,所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络的粒径分布为0.25~0.85mm,平均孔径为8~40nm,活性氨基含量0.6~2.2mmol/g,平均比表面积为150~1000m2/g,总孔容为0.5~1.3cm3/g。
优选地,所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络的粒径分布为0.25~0.85mm,平均孔径为8.95~33.1nm,活性氨基含量0.65~2.13mmol/g,平均比表面积为150.2~512.1m2/g,总孔容为0.66~1.25cm3/g。
本发明还公开了上述亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络的制备方法,包括如下步骤:
(1)采用悬浮聚合法制得第一网交联聚丙烯酸甲酯二乙烯基苯白球;
(2)用含苯乙烯和二乙烯基苯组成的混合溶液将步骤(1)制得的第一网交联聚丙烯酸甲酯二乙烯基苯白球充分溶胀,再将溶胀后的第一网交联聚丙烯酸甲酯二乙烯基苯白球分散在水中反应制得聚丙烯酸甲酯与聚苯乙烯互穿聚合物网络;
(3)将步骤(2)制得的聚丙烯酸甲酯与聚苯乙烯互穿聚合物网络进行胺化反应,获得亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络。
优选地,步骤(1)采用悬浮聚合法制得第一网交联聚丙烯酸甲酯二乙烯基苯白球的具体步骤是:将含有分散剂的水相加入反应容器中加热,向水相中加入油相后,在氮气气氛下反应,所述的油相由单体、交联剂、致孔剂和引发剂组成,反应完成后进行洗涤、干燥,得到第一网交联聚丙烯酸甲酯二乙烯基苯白球。
进一步的,所述的单体和交联剂质量之和与致孔剂的质量比为1:3~3:1,单体与交联剂的质量比为1:3~3:1,所述的致孔剂包括良溶剂和非良溶剂,良溶剂与非良溶剂的质量比为1:4~4:1,单体与引发剂的质量比为100:1~200:1,所述的单体为丙烯酸甲酯,交联剂为二乙烯基苯,良溶剂为甲苯和/或二甲苯,引发剂为过氧化苯甲酰,非良溶剂选自正庚烷、正辛烷和环己烷中的一种以上。
优选地,步骤(2)中所述的苯乙烯和二乙烯基苯组成的混合物中苯乙烯与二乙烯基苯的质量比为1:3~3:1。
优选地,步骤(3)的具体步骤是:用多乙烯多胺充分溶胀聚丙烯酸甲酯与聚苯乙烯互穿聚合物网络后,在120℃~160℃下进行胺化反应8~12h,获得亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络。
进一步的,所述的多乙烯多胺选自二乙烯三胺、三乙烯四胺和四乙烯五胺中的一种,所述的多乙烯多胺的质量与聚丙烯酸甲酯与聚苯乙烯互贯聚合物网络的质量比为2:1~5:1。
本发明还公开了亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络在秸秆水解液脱除发酵抑制物中的应用。
亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络在秸秆水解液脱除发酵抑制物中的应用,具体包括如下步骤:
(1)取木质纤维素制成木质纤维素水解液,水解液中还原糖浓度为2.4%~5.5%,有机酸浓度为0.35%~1.1%,醛类物质浓度为0.1%~0.5%,酸溶木质素浓度0.4%~0.65%,使用碱性物质将木质纤维素水解液的pH调节至1~6,过滤,得到上清液;
(2)将所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络以所述的上清液质量0.5~20%的添加量加入到上清液中,进行震荡和过滤,得到的滤液即为已去除发酵抑制物的木质纤维素水解液。
所述的木质纤维素选自稻草、甘蔗渣、小麦秸秆、玉米芯、玉米秸秆、水稻秸秆和棉花秆中的一种以上。所述的碱性物质选自石灰、氢氧化钠、氢氧化钾、碳酸钙、碳酸钠和碳酸钾中的一种以上。
亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络在处理秸秆水解液后,其可以通过洗脱剂洗脱再生,再生方法的具体步骤是以亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络质量的10~50倍的洗脱剂在25℃~45℃的恒温摇床中振荡10~50min进行洗脱,过滤,得到再生后的亲水/疏水转换的聚丙烯酰胺与聚苯乙烯互穿聚合物和低碳醇洗脱液;低碳醇洗脱液经常压蒸馏或减压精馏回收利用。
上述洗脱剂中,低碳醇的体积分数为20~100%;低碳醇选自甲醇、乙醇和异丙醇中的一种以上,或低碳醇选自甲醇、乙醇、丙醇和异丙醇中的一种以上和水的混合物。
与现有技术相比,本发明的有益效果是:
1、本发明通过制备聚丙烯酰胺与聚苯乙烯类互穿聚合物网络,引入了亲水性酰胺基团和疏水性官能团,对秸秆水解液进行脱毒处理,能够与水解液中的亲水性发酵抑制物形成分子间氢键,去除大部分的亲水性发酵抑制物,减少了秸秆稀酸水解副产物的含量。
2、丙烯酰胺是强致癌物质,本发明制备亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物过程中避免了使用丙烯酰胺等强致癌物质,而是通过胺解过程实现酰胺基官能团的修饰目的,制备过程较环保绿色。
3、本发明制备的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络孔结构和极性可在较大范围内定向调控,具有高选择性、高吸附容量、洗脱再生容易等优点,从而显著提高了对秸秆水解液的脱毒效果。与此同时,对秸秆水解液中的糖类物质吸附不多,得到的水解液作为微生物生长的发酵培养基,缩短了发酵周期,提高了发酵效率,降低秸秆水解液脱毒成本和微生物发酵成本;且脱毒过程设备投资小、运行成本低、能耗低、操作简单、不会产生二次污染,是一种绿色脱毒工艺。
附图说明
图1是本发明实施例1制得亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络SEM图;
图2是本发明实施例1木质纤维素水解液吸附前后比较。
具体实施方式
以下实施例是对本发明的进一步说明,而不是对本发明的限制。
实施例1
(1)制备亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络
依以下步骤制备亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络:
1)悬浮聚合法制备第一网交联聚丙烯酸甲酯二乙烯基苯白球
将水相240mL(水相中含有质量分数为1.0%的聚乙烯醇和3-5滴质量分数为1%的亚甲基蓝溶液)加入带有机械搅拌、温度计和蛇形冷凝管的500mL三口烧瓶中,置于油浴中加热至50℃后,向水相中加入油相(依次加入丙烯酸甲酯单体26.7g,二乙烯基苯13.3g,甲苯20g,正庚烷20g和过氧化苯甲酰0.4g),通入氮气5min后,调节搅拌速度为160rpm,控制油滴大小。之后缓慢升温至80℃,反应5h,反应结束后,所得的产物分别用热水与工业酒精交替洗涤数次至洗涤液澄清;再用质量分数为95%的工业酒精在索氏提取器中进行提取24h后,置于60℃真空干燥至恒重,得到第一网交联聚丙烯酸甲酯二乙烯基苯白球。
2)制备聚丙烯酸甲酯与聚苯乙烯互穿聚合物网络
将上述制得第一网交联聚丙烯酸甲酯二乙烯基苯白球10g加入150mL具塞锥形瓶中;再加入由苯乙烯30g、二乙烯基苯30g和过氧化苯甲酰0.3g组成的混合物在室温下溶胀过夜,然后,将多余的油相抽滤。将水相210mL(水相中含有质量分数为1.0%的聚乙烯醇)加入带有机械搅拌、温度计和蛇形冷凝管的500mL三口烧瓶中,置于油浴中加热至60℃后,加入溶胀后的第一网交联聚丙烯酸甲酯二乙烯基苯白球,调节转速为160rpm搅拌2h后,升温至80℃,然后2h升温至90℃,1h后升温至95℃,回流反应6h。反应结束后,所得的产物分别用热水与工业酒精交替洗涤数次至洗涤液澄清;再用质量分数为95%的工业酒精在索氏提取器中进行提取24h后,置于60℃真空干燥至恒重,得到聚丙烯酸甲酯聚苯乙烯互穿聚合物网络。
3)胺化反应制备亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络
将上述制备的聚丙烯酸甲酯聚苯乙烯互穿聚合物网络10g置于150mL三口瓶中,再加入二乙烯三胺50g,溶胀2h,将溶胀后的聚丙烯酸甲酯聚苯乙烯互穿聚合物网络然后逐步升温至120℃,反应10h。结束后冷却,产物用5%的NaCl溶液洗涤(称取1900g去离子水,加入100g NaCl,搅拌至完全溶解),再用大量去离子水冲洗至中性。再用质量分数为95%的工业酒精在索氏提取器中进行提取24h后,置于60℃真空干燥至恒重,得到亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络。测试得亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络BET比表面积为319.5m2/g,孔容为1.21cm3/g,平均孔径为10.87nm,活性氨基含量2.13mmol/g。
图1为本实施例制得亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络SEM图;从图1中可以看出,互穿聚合物网络是球状颗粒,表面有大量孔隙存在。
(2)亲水/疏水聚丙烯酰胺聚苯乙烯互穿聚合物网络应用在秸秆水解液脱除发酵抑制物
依以下步骤对木质纤维素水解液进行精制:
1)采取碳酸钙将甘蔗渣水解液pH调节至6,过滤,得到上清液。经测定,上清液在540nm处吸光度为0.651,由葡萄糖8.66g/L、木糖30.88g/L、阿拉伯糖2.31g/L、甲酸1.64g/L、乙酸6.31g/L、乙酰丙酸2.92g/L、5-羟甲基糠醛0.50g/L、糠醛3.01g/L和酸溶木质素6.45g/L等组成。
2)将亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络1.0g和上述上清液50mL置于100mL具塞锥形瓶中,置于160rpm、25℃的恒温摇床振荡3h;达吸附平衡后,过滤,得到的滤液即为已去除发酵抑制物的秸秆水解液。
利用紫外-可见分光光度计测定已去除发酵抑制物的秸秆水解液脱色率、酸溶木质素去除率分别为60.7%和54.0%,利用液相色谱法测定总糖回收率为97.4%,甲酸、乙酸和乙酰丙酸去除率分别为18.9%,7.4%和17.5%,HMF和糠醛去除率分别为25.1%和49.22%,酸溶木质素去除率为58.9%。
图2是木质纤维素水解液吸附前后比较。从图2可以看出,木质纤维素水解液经亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络吸附后,水解液色素含量显著降低。
实施例2
与实施例1相比,不同之处在于:制备亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络的过程中,步骤(2)中苯乙烯与二乙烯基苯的质量比为3:1,步骤(3)中多乙烯多胺为三乙烯四胺,三乙烯四胺的质量是聚丙烯酸甲酯聚苯乙烯互穿聚合物网络的2倍,在140℃下胺化反应8h。
将上述制得亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络用于木质纤维素水解液脱除发酵抑制物,具体步骤是:
1)采取氢氧化钠将稻草水解液pH调节至1,过滤,得到上清液。经测定,上清液在540nm处吸光度为0.921,由葡萄糖11.65g/L、木糖23.98g/L、阿拉伯糖3.21g/L、甲酸0.99g/L、乙酸1.77g/L、乙酰丙酸1.67g/L、5-羟甲基糠醛0.61g/L、糠醛0.78g/L和酸溶木质素6.08g/L等组成。
2)将亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络0.25g和上述上清液50g置于100mL具塞锥形瓶中,置于160rpm、15℃的恒温摇床振荡5h;达吸附平衡后,过滤,得到的滤液即为已去除发酵抑制物的秸秆水解液。
实施例3
与实施例1相比,不同之处在于:制备亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络的过程中,步骤(2)中苯乙烯与二乙烯基苯的质量比为1:3,步骤(3)中多乙烯多胺为三乙烯四胺,三乙烯四胺的质量是聚丙烯酸甲酯聚苯乙烯互穿聚合物网络的3倍,在150℃下胺化反应12h。
将上述制得亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络用于木质纤维素水解液脱除发酵抑制物,具体步骤是:
1)采取氢氧化钾将小麦秸秆水解液pH调节至3,过滤,得到上清液。经测定,上清液在540nm处吸光度为0.783,由葡萄糖5.02g/L、木糖22.13g/L、阿拉伯糖1.73g/L、甲酸0.91g/L、乙酸3.47g/L、乙酰丙酸1.62g/L、5-羟甲基糠醛0.31g/L、糠醛0.60g/L和酸溶木质素4.02g/L等组成。
2)将亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络10g和上述上清液50g置于100mL具塞锥形瓶中,置于160rpm、45℃的恒温摇床振荡0.5h;达吸附平衡后,过滤,得到的滤液即为已去除发酵抑制物的秸秆水解液。
实施例4~6
(1)制备亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络
如表1所示,与实施例1相比,实施例4~6除第一网交联聚丙烯酸甲酯二乙烯基苯白球制备过程中丙烯酸甲酯与二乙烯基苯配比调整之外,其余实验条件及聚丙烯酸甲酯与聚苯乙烯互穿聚合物制备步骤及胺化步骤均相同。得到的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络的BET总表面积、总孔容、平均孔径和活性氨基数量列于表1中。
表1实施例4~6制备工艺条件与结果
(2)亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络应用在秸秆水解液脱除发酵抑制物
实施例4~6与实施例1实施步骤相同。
使用实施例4得到的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络处理甘蔗渣水解液,利用紫外-可见分光光度计测定处理后的水解液脱色率、酸溶木质素去除率分别为65.8%和60.2%,利用液相色谱法测定总糖回收率为96.8%,甲酸、乙酸和乙酰丙酸去除率分别为20.1%,8.1%和19.7%,HMF和糠醛去除率分别为27.9%和53.9%,酸溶木质素去除率为62.1%。
使用实施例5得到的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络处理甘蔗渣水解液,利用紫外-可见分光光度计测定处理后的水解液脱色率、酸溶木质素去除率分别为70.6%和69.4%,利用液相色谱法测定总糖回收率为95.9%,甲酸、乙酸和乙酰丙酸去除率分别为22.5%,10.1%和21.6%,HMF和糠醛去除率分别为30.5%和58.5%,酸溶木质素去除率为63.5%。
使用实施例6得到的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络处理甘蔗渣水解液,利用紫外-可见分光光度计测定处理后的水解液脱色率、酸溶木质素去除率分别为61.2%和55.2%,利用液相色谱法测定总糖回收率为98.4%,甲酸、乙酸和乙酰丙酸去除率分别为19.5%,8.2%和18.9%,HMF和糠醛去除率分别为26.6%和50.8%,酸溶木质素去除率为57.3%。
实施例7~10
(1)制备亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络
如表2所示,与实施例1相比,实施例7~10对第一网交联聚丙烯酸甲酯二乙烯基苯白球制备丙烯酸甲酯与致孔剂(良溶剂+非良溶剂)的配比进行了调整,致孔剂中良溶剂与非良溶剂比例进行了调整,具体工艺条件变动如表2所示,其余实验条件及聚丙烯酸甲酯与聚苯乙烯互穿聚合物制备步骤及胺化步骤均相同。
表2实施例7~10制备工艺条件
将实施例7~10得到的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络测得的BET总表面积、总孔容、平均孔径和活性氨基数量列于表3中,如表3所示。
表3实施例7~10测试结果
(2)亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络应用在秸秆水解液脱除发酵抑制物
实施例7与实施例1实施步骤相同。使用实施例7得到的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络处理甘蔗渣水解液,利用紫外-可见分光光度计测定处理后的水解液脱色率、酸溶木质素去除率分别为26.8%和27.0%,利用液相色谱法测定总糖回收率为98.9%,甲酸、乙酸和乙酰丙酸去除率分别为5.1%,1.7%和8.5%,HMF和糠醛去除率分别为11.2%和19.9%,酸溶木质素去除率为23.5%。
实施例8与实施例1实施步骤相同。使用实施例8得到的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络处理甘蔗渣水解液,利用紫外-可见分光光度计测定处理后的水解液脱色率、酸溶木质素去除率分别为25.8%和29.4%,利用液相色谱法测定总糖回收率为98.2%,甲酸、乙酸和乙酰丙酸去除率分别为8.2%,3.2%和6.9%,HMF和糠醛去除率分别为12.6%和25.6%,酸溶木质素去除率为31.8%。
实施例9与实施例1实施步骤相同,不同的是亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络添加量为2g。
使用实施例9得到的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络处理甘蔗渣水解液,利用紫外-可见分光光度计测定处理后的水解液脱色率、酸溶木质素去除率分别为69.7%和75.2%,利用液相色谱法测定总糖回收率为94.2%,甲酸、乙酸和乙酰丙酸去除率分别为29.1%,10.6%和22.4%,HMF和糠醛去除率分别为35.2%和60.3%,酸溶木质素去除率为65.3%。
实施例10与实施例1实施步骤相同,不同的是亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络添加量为2g,吸附温度为35℃。
使用实施例10得到的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络处理甘蔗渣水解液,利用紫外-可见分光光度计测定处理后的水解液脱色率、酸溶木质素去除率分别为52.7%和63.2%,利用液相色谱法测定总糖回收率为94.7%,甲酸、乙酸和乙酰丙酸去除率分别为20.1%,6.9%和18.8%,HMF和糠醛去除率分别为26.7%和55.9%,酸溶木质素去除率为59.1%。
以上仅是本发明的优选实施方式,应当指出的是,上述实施方式不应视为对本发明的限制,本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说,在不脱离本发明的精神和范围内,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (9)
1.一种亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络,其特征在于,所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络的粒径分布为0.25~0.85mm,平均孔径为8~40nm,活性氨基含量0.6~2.2mmol/g,平均比表面积为150~1000m2/g,总孔容为0.5~1.3cm3/g;所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络的制备方法,包括如下步骤:
(1)采用悬浮聚合法制得第一网交联聚丙烯酸甲酯二乙烯基苯白球;
(2)用含苯乙烯和二乙烯基苯组成的混合物将步骤(1)制得的第一网交联聚丙烯酸甲酯二乙烯基苯白球充分溶胀,再将溶胀后的第一网交联聚丙烯酸甲酯二乙烯基苯白球分散在水中反应制得聚丙烯酸甲酯与聚苯乙烯互穿聚合物网络;
(3)将步骤(2)制得的聚丙烯酸甲酯与聚苯乙烯互穿聚合物网络进行胺化反应,获得亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络。
2.根据权利要求1所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络,其特征在于,所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络的粒径分布为0.25~0.85mm,平均孔径为8.95~33.1nm,活性氨基含量0.65~2.13mmol/g,平均比表面积为150.2~512.1m2/g,总孔容为0.66~1.25cm3/g。
3.根据权利要求1所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络,其特征在于,步骤(1)采用悬浮聚合法制得第一网交联聚丙烯酸甲酯二乙烯基苯白球的具体步骤是:将含有分散剂的水相加入反应容器中加热,向水相中加入油相后,在氮气气氛下反应,所述的油相由单体、交联剂、致孔剂和引发剂组成,反应完成后进行洗涤、干燥,得到第一网交联聚丙烯酸甲酯二乙烯基苯白球。
4.根据权利要求3所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络,其特征在于,所述的单体和交联剂质量之和与致孔剂的质量比为1:3~3:1,单体与交联剂的质量比为1:3~3:1,所述的致孔剂包括良溶剂和非良溶剂,良溶剂与非良溶剂的质量比为1:4~4:1,单体与引发剂的质量比为100:1~200:1,所述的单体为丙烯酸甲酯,交联剂为二乙烯基苯,良溶剂为甲苯和/或二甲苯,引发剂为过氧化苯甲酰,非良溶剂选自正庚烷、正辛烷和环己烷中的一种以上。
5.根据权利要求1所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络,其特征在于,步骤(2)中所述的苯乙烯和二乙烯基苯组成的混合物中苯乙烯与二乙烯基苯的质量比为1:3~3:1。
6.根据权利要求1所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络,其特征在于,步骤(3)的具体步骤是:用多乙烯多胺充分溶胀聚丙烯酸甲酯与聚苯乙烯互穿聚合物网络后,在120℃~160℃下进行胺化反应8~12h,获得亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络。
7.根据权利要求6所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络,其特征在于,所述的多乙烯多胺选自二乙烯三胺、三乙烯四胺和四乙烯五胺中的一种,所述的多乙烯多胺的质量与聚丙烯酸甲酯与聚苯乙烯互贯聚合物网络的质量比为2:1~5:1。
8.权利要求1所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络在秸秆水解液脱除发酵抑制物中的应用。
9.根据权利要求8所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络在秸秆水解液脱除发酵抑制物中的应用,其特征在于,包括如下步骤:
(1)取木质纤维素制成木质纤维素水解液,水解液中还原糖浓度为2.4%~5.5%,有机酸浓度为0.35%~1.1%,醛类物质浓度为0.1%~0.5%,酸溶木质素浓度0.4%~0.65%,使用碱性物质将木质纤维素水解液的pH调节至1~6,过滤,得到上清液;
(2)将所述的亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络以所述的上清液质量的0.5~20%的添加量加入到上清液中,进行震荡和过滤,得到的滤液即为已去除发酵抑制物的木质纤维素水解液。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910470421.3A CN110183553B (zh) | 2019-05-31 | 2019-05-31 | 一种亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910470421.3A CN110183553B (zh) | 2019-05-31 | 2019-05-31 | 一种亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110183553A CN110183553A (zh) | 2019-08-30 |
CN110183553B true CN110183553B (zh) | 2021-12-03 |
Family
ID=67719570
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910470421.3A Active CN110183553B (zh) | 2019-05-31 | 2019-05-31 | 一种亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110183553B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112745776A (zh) * | 2021-01-08 | 2021-05-04 | 上海佳衡胶粘制品有限公司 | 便于清理的胶带及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050281999A1 (en) * | 2003-03-12 | 2005-12-22 | Petritech, Inc. | Structural and other composite materials and methods for making same |
CN103319662A (zh) * | 2013-06-28 | 2013-09-25 | 中南大学 | 一种疏水/亲水性交联聚二乙烯苯/聚丙烯酰多乙烯多胺互贯聚合物网络及其制备方法 |
-
2019
- 2019-05-31 CN CN201910470421.3A patent/CN110183553B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050281999A1 (en) * | 2003-03-12 | 2005-12-22 | Petritech, Inc. | Structural and other composite materials and methods for making same |
CN103319662A (zh) * | 2013-06-28 | 2013-09-25 | 中南大学 | 一种疏水/亲水性交联聚二乙烯苯/聚丙烯酰多乙烯多胺互贯聚合物网络及其制备方法 |
Non-Patent Citations (1)
Title |
---|
《互穿网络改性的蛋白质印迹海藻酸钙微球的制备与表征》;英晓光等;《天津大学学报》;20110215;第44卷(第2期);第134-140页 * |
Also Published As
Publication number | Publication date |
---|---|
CN110183553A (zh) | 2019-08-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Krasňan et al. | Immobilization of cells and enzymes to LentiKats® | |
CN108355626B (zh) | 一种改性苯乙烯系吸附树脂、其制备方法及其在木质纤维素水解液的精制上的应用 | |
Tan et al. | Immobilization of β-glucosidase from Aspergillus niger on κ-carrageenan hybrid matrix and its application on the production of reducing sugar from macroalgae cellulosic residue | |
CN1914120B (zh) | 发酵产品的制备 | |
CN107337764B (zh) | 玉米秸穰半纤维素基疏水温敏凝胶的制备方法及应用 | |
EP3347481B1 (en) | Process for the purification of biomass hydrolysate | |
CN113398901B (zh) | 一种生物质基热敏仿生水凝胶吸附材料及其制备方法和应用 | |
MXPA05001214A (es) | Uso de agentes de floculacion para separar los residuos solidos en sustratos de fermentacion hidrolisados. | |
CA3127968C (en) | Amphoteric biomass-based hyperbranched adsorption material to multiple heavy metal ions and preparation method and use thereof | |
CN107243330B (zh) | 一种用酒糟制备的两性吸附剂及其制备方法和应用 | |
Chen et al. | Improved enzymatic saccharification of bulrush via an efficient combination pretreatment | |
CN110183553B (zh) | 一种亲水/疏水聚丙烯酰胺与聚苯乙烯互穿聚合物网络及其应用 | |
Chen et al. | Synthesis of polyacrylamide/polystyrene interpenetrating polymer networks and the effect of textural properties on adsorption performance of fermentation inhibitors from sugarcane bagasse hydrolysate | |
CN107417842A (zh) | 一种中极性大孔吸附树脂及其在去除木质纤维素水解液中酸溶木质素的应用 | |
CN103602656A (zh) | 一种制备固定化酶和固定化菌种的方法 | |
CN108976481B (zh) | 一种硫脲改性的纤维素基水凝胶及其制备方法 | |
CN108295818A (zh) | 一种利用氨基硫脲修饰竹浆纤维素制备重金属离子吸附材料的方法 | |
CN112500527A (zh) | 有机改性粉煤灰增强海藻酸钠水凝胶的制备方法 | |
Ariaeenejad et al. | Improved saccharification of rice straw by removing phenolic compounds using a stable immobilized metagenome-derived laccase on sodium alginate-based hydrogel | |
CN109749023A (zh) | 一种pH响应改性木质素纳米胶束的制备方法 | |
CN111359594B (zh) | 一种硼酸吸附材料及制备方法 | |
CN111468080B (zh) | 一种工业废水的环保处理方法及处理剂 | |
CN110586039B (zh) | 一种可用光照再生的生物质吸附剂及其制备方法和应用 | |
Ribeiro et al. | Biosorption of phenolic compounds in lignocellulosic biomass biorefineries | |
CN110975844B (zh) | 一种聚天冬氨酸接枝粘胶纤维吸附剂的制备方法 |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |