CN107986378A - 一种去除制浆造纸废液中草酸根的方法 - Google Patents

一种去除制浆造纸废液中草酸根的方法 Download PDF

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CN107986378A
CN107986378A CN201810010715.3A CN201810010715A CN107986378A CN 107986378 A CN107986378 A CN 107986378A CN 201810010715 A CN201810010715 A CN 201810010715A CN 107986378 A CN107986378 A CN 107986378A
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李海龙
葛淑娟
刘梦茹
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South China University of Technology SCUT
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041Oxides or hydroxides
    • 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
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • C02F2103/26Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

本发明公开了一种去除制浆造纸废液中草酸根的方法,包括以下步骤:(1)将层状双金属氢氧化物进行焙烧,焙烧后,将其冷却备用;(2)将焙烧后得到的产物加入到制浆造纸废液中,进行吸附处理。本发明采用层状双金属氢氧化物作为吸附剂去除制浆造纸废液中草酸根具有适用范围广,操作步骤简单,易于控制;吸附能力强且吸附量高,可以有效降低制浆造纸废液中草酸根含量;可循环利用,廉价易得,便于运输与保存,具有经济性与环保性等优点。

Description

一种去除制浆造纸废液中草酸根的方法
技术领域
本发明涉及一种去除制浆造纸废液中草酸根的方法,属于制浆造纸领域。
背景技术
在制浆造纸过程中,草酸根的来源途径众多,不仅来自于原料的本身,还来自于部分木素及碳水化合物的降解。草酸根对制浆造纸过程有着显著的影响,其危害常表现在:(1)在制浆漂白过程中,其可与钙等碱土金属离子形成草酸盐垢,造成输送管道及洗涤筛选等设备的堵塞,影响设备的正常运行;(2)在黑液蒸发和浓缩过程中,其与钠离子在蒸发器的内表面形成草酸钠垢,降低蒸发器效率;(3)在施胶过程中,其与铝离子结合形成草酸铝,消耗有效铝离子,从而导致松香酸铝的形成量减少,影响施胶效果。因此,降低废液中草酸根含量具有现实意义。
层状双金属氢氧化物是由两种或两种以上的金属元素组成的具有水滑石层状晶体结构的氢氧化物,作为一类重要的无机功能材料,以其独特的结构和性质受到广泛的关注。一方面,层状双金属氢氧化物的层状结构使其具有较大的比表面积,且层间阴离子具有可交换性;另一方面,层状双金属氢氧化物焙烧之后具有独特的“记忆效应”,并且比表面积增大。除此之外,层状双金属氢氧化物廉价易得,对废液环境要求低,易于分离,可循环利用。
传统控制制浆造纸过程中草酸根形成的方法是通过控制浆料品种、改善蒸煮漂白工艺条件以及利用生物酶处理等方式。前两者会对纸浆的性能产生一定的影响,而生物酶处理对环境要求较高,高温强碱下易于使其失活,且昂贵难以制取。因此,寻求一种去除制浆造纸废液中草酸根的新方法显得尤为重要。
发明内容
本发明针对草酸根带来的问题以及现有技术的不足,提出了一种利用层状双金属氢氧化物去除制浆造纸废液中草酸根的方法。该方法采用层状双金属氢氧化物焙烧之后得到的产物作为吸附剂,吸附草酸根,与现有技术相比,具有去除草酸根效果好,适用范围广,可循环利用,廉价易得等特点。
本发明的目的通过如下技术方案实现:
一种去除制浆造纸废液中草酸根的方法,包括以下步骤:
(1)层状双金属氢氧化物的焙烧
将层状双金属氢氧化物(LDHs)进行焙烧,焙烧后,将其冷却备用;
(2)对制浆造纸废液的处理
将焙烧后得到的产物加入到制浆造纸废液中,进行吸附处理。
上述方法还包括如下回收循环利用步骤:步骤(2)完成后,进行固液分离,分离得到的固体,重复步骤(1)与(2),继续进行吸附处理。
优选地,步骤(1)所述焙烧的温度为400-600℃;时间为3-24h。
优选地,步骤(1)所述的层状双金属氢氧化物,是由镁、铝、镍、锌、铁和锰中两种或两种以上的金属元素组成的;其层间阴离子为碳酸根离子、草酸根离子或硝酸根离子。
优选地,步骤(1)所述的层状双金属氢氧化物为MgAl-C2O4-LDHs、MgAl-CO3-LDHs、MgAl-NO3-LDHs或NiAl-NO3-LDHs。
优选地,步骤(2)所述焙烧之后得到的产物与制浆造纸废液的固液比为1:100-1:1000g/mL。
优选地,步骤(2)所述吸附处理的温度为30-70℃,时间为10-360min。
与现有技术相比,本发明采用层状双金属氢氧化物作为吸附剂去除制浆造纸废液中草酸根具有如下优点:
(1)本发明适用范围广,操作步骤简单,易于控制。
(2)吸附能力强且吸附量高,可以有效降低制浆造纸废液中草酸根含量。
(3)可循环利用,廉价易得,便于运输与保存,具有经济性与环保性。
具体实施方式
下面结合实施例对本发明作进一步详细说明。本发明并不局限于以下实施方式。
实施例1
利用层状双金属氢氧化物去除制浆造纸废液中草酸根的方法,具体包括以下步骤:
(1)将MgAl-C2O4-LDHs在450℃下焙烧8h,冷却后,备用。
(2)将焙烧之后得到的产物加入到制浆造纸废液中(固液比为1:300(g/mL)),在30℃下处理120min。
(3)步骤(2)完成后,采用自然沉降法对其进行固液分离,将分离得到的固体,贮存备用。
实验结果表明,其吸附量为151.67mg/g。
实施例2
利用层状双金属氢氧化物去除制浆造纸废液中草酸根的方法,具体包括以下步骤:
(1)将NiAl-NO3-LDHs在600℃下焙烧24h,冷却后,备用。
(2)将焙烧之后得到的样品加入到制浆造纸废液中(固液比为1:1000g/mL),在50℃下处理150min。
(3)步骤(2)完成后,采用自然沉降法对其进行固液分离,将分离得到的固体,贮存备用。
实验结果表明,其吸附量为109.69mg/g。
实施例3
利用层状双金属氢氧化物去除制浆造纸废液中草酸根的方法,具体包括以下步骤:
(1)将MgAl-CO3-LDHs在550℃下焙烧3h,冷却后,备用。
(2)将焙烧之后得到的产物加入到制浆造纸废液中(固液比为1:100g/mL),在70℃下处理360min。
(3)步骤(2)完成后,采用离心分离法对其进行固液分离,将分离得到的固体,贮存备用。
实验结果表明,其吸附量为144.78mg/g。
实施例4
利用层状双金属氢氧化物去除制浆造纸废液中草酸根的方法,具体包括以下步骤:
(1)将MgAl-CO3-LDHs在400℃下焙烧12h,冷却后,备用。
(2)将焙烧之后得到的产物加入到制浆造纸废液中(固液比为1:800g/mL),在70℃下处理30min。
(3)步骤(2)完成后,采用离心分离法对其进行固液分离,将分离得到的固体,贮存备用。
实验结果表明,其吸附量为207.43mg/g。
实施例5
利用层状双金属氢氧化物去除制浆造纸废液中草酸根的方法,具体包括以下步骤:
(1)将MgAl-CO3-LDHs在500℃下焙烧4h,冷却后,备用。
(2)将焙烧之后得到的产物加入到制浆造纸废液中(固液比为1:200g/mL),在50℃下处理90min。
(3)步骤(2)完成后,采用过滤分离法对其进行固液分离,将分离得到的固体,重复步骤(1)与(2)。
实验结果:
上述实施例仅用于解释本发明,而非限制本发明,对于层状双金属氢氧化物去除制浆造纸废液中草酸根的简单变化均应属于本发明的保护范围。

Claims (7)

1.一种去除制浆造纸废液中草酸根的方法,其特征在于,包括以下步骤:
(1)层状双金属氢氧化物的焙烧
将层状双金属氢氧化物进行焙烧,焙烧后,将其冷却备用;
(2)对制浆造纸废液的处理
将焙烧后得到的产物加入到制浆造纸废液中,进行吸附处理。
2.根据权利要求1所述的方法,其特征在于,还包括如下回收循环利用步骤:步骤(2)完成后,进行固液分离,分离得到的固体,重复步骤(1)与(2),继续进行吸附处理。
3.根据权利要求1或2所述的方法,其特征在于,步骤(1)所述焙烧的温度为400-600oC;时间为3-24h。
4.根据权利要求1或2所述的方法,其特征在于,步骤(1)所述的层状双金属氢氧化物,是由镁、铝、镍、锌、铁和锰中两种或两种以上的金属元素组成的;其层间阴离子为碳酸根离子、草酸根离子或硝酸根离子。
5.根据权利要求1或2所述的方法,其特征在于,步骤(1)所述的层状双金属氢氧化物为MgAl-C2O4-LDHs、MgAl-CO3-LDHs、MgAl-NO3-LDHs或NiAl-NO3-LDHs。
6.根据权利要求1或2所述的方法,其特征在于,步骤(2)所述焙烧之后得到的产物与制浆造纸废液的固液比为1:100-1:1000g/mL。
7.根据权利要求1或2所述的方法,其特征在于,步骤(2)所述吸附处理的温度为30-70℃,时间为10-360min。
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Application publication date: 20180504