CN113086958B - 一种高炉渣基复合材料的制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title abstract description 22
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- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 29
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- 238000009628 steelmaking Methods 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims 1
- 229910000389 calcium phosphate Inorganic materials 0.000 claims 1
- 235000019700 dicalcium phosphate Nutrition 0.000 claims 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims 1
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- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims 1
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- 235000015497 potassium bicarbonate Nutrition 0.000 claims 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 235000011181 potassium carbonates Nutrition 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid 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
- B01J20/048—Solid 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 containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
本发明公开了一种高炉渣基复合材料的制备方法,属于工业废渣回收再利用技术领域。本发明主要包括以下步骤:(1)高炉渣的碱融,(2)与磷酸盐反应,(3)水热陈化,制备得到附加值高的高炉渣基羟基磷灰石‑沸石复合材料,实现了高炉渣中有用成分的综合利用。本发明的方法,具有适应性强、工艺简单、操作方便、反应条件温和、产品附加值高等特点;本发明的方法,以高炉渣为廉价原料,既能有效缓解高炉渣的大量堆存引发的环境问题,又能在一定程度上降低企业堆场建设运营费用。
Description
技术领域
本发明属于工业废渣回收再利用技术领域,主要涉及一种高炉渣基复合材料的制备方法,具体为一种高炉渣基羟基磷灰石-沸石复合材料的制备方法。
背景技术
高炉渣作为髙炉炼铁的主要副产品,其主要由铁矿石中的脉石、焦炭中的灰分、助熔剂和其他不能进入生铁中的杂质组成。随着我国钢铁工业的发展,高炉渣的排放量日益增大,高炉渣的大量排出和堆放,如果不加大力度对其进行合理的资源化利用,不仅会造成大量的资源浪费,而且大量的堆积势必会造成大量土地资源的侵占和环境污染等问题。因此,高炉渣的排放已经成为钢铁生产企业、社会的一个难题,如何安全处置和高效利用这些“高炉渣山”成为一个亟待解决的重大问题。
目前,我国高炉渣的综合利用率和世界发达国家相比依然较低,近年来,针对高炉渣资源化的问题,不少学者进行了有益探索,设计发展出了以下利用途径:
专利CN106185975A公开了一种利用高炉渣制备分子筛晶体的方法,其主要包括以下步骤:(1)高炉渣的预处理,(2)与盐酸反应,(3)与氢氧化钠反应,(4)采用水热法制备具有多孔结构的分子筛晶体。最终得到高附加值的纯度92%以上的硅胶和95%以上偏铝酸盐和纯度90%以上的分子筛晶体。其记载的技术方案在制备过程中主要利用的高炉渣成分为SiO2,Al2O3,并不涉及CaO的利用,另外,其工艺步骤过多,其中会大量且无意义的消耗盐酸;同时,其分子筛产品的制备是在高压釜内以较高的温度(120-200℃)和高压下进行,制备过程的能耗较高、存在制备成本高、经济效益差的问题。
专利CN101397154B公开了一种利用高炉渣制备的水处理剂的方法,其为通过碱性溶液处理高炉渣而得到,将高炉渣和pH>11的碱性水溶液按照固液比为1:1-5混和,过滤后在50~120℃干燥24~48h,取出,粉碎,最后过100目的标准筛,制备得到改良的高炉渣基水处理剂。其记载的技术方案在制备高炉渣基水处理剂时,采用的是碱性水溶液对高炉渣进行碱融处理,由于矿物原料中的一些稳定的结晶相,如石英、莫来石等结晶体,很难完全溶解于碱溶液中进而导致凝胶结晶过程是在没有完全溶解的矿物颗粒表面进行,不可避免存在产品结晶度不高、晶相不均一的问题,且高炉渣资源利用率低。
因此,上述公开专利文本中记载的高炉渣处理方案,受到产品产量、附加值、工艺技术条件和成本的限制,工业化利用方面进展缓慢,在实际工业生产中存在高炉渣利用效率低、工艺复杂、成本高、经济效益差、环境风险高等问题,难以满足对高炉渣资源利用之需求,严重制约了资源综合利用水平的提升。
发明内容
本发明的目的是提供一种高炉渣基复合材料的制备方法,充分利用高炉渣中的有效成分制备形成一种高炉渣基羟基磷灰石-沸石复合材料,该方法具有适应性强、工艺简单、操作方便、反应条件温和、产品附加值高等特点,解决了现有技术中存在的闲置堆存高炉渣的开发利用成本高、高炉渣资源化效率低的问题。
本发明提供一种高炉渣基复合材料的制备方法,包括下述步骤:
步骤一:将高炉渣与碱性介质颗粒在高温下熔融得到熔融产物;
步骤二:所述熔融产物与磷酸盐溶液反应后,加入NaOH溶液充分混合后晶化,得到晶化产品;
步骤三:将所述晶化产品取出过滤,水洗滤饼至中性,干燥后制备得到所述高炉渣基复合材料。
本发明所述一种高炉渣基复合材料的制备方法,步骤一中,为充分利用高炉渣中的有用成分,采用碱性介质颗粒对高炉渣进行碱融处理,将高炉渣中的难处理的硅铝质转变为可溶性的硅酸盐及偏铝酸盐,以提高反应活性,降低反应时间,碱性介质颗粒高温熔融后对高炉渣进行碱融处理,本申请采用碱性介质颗粒相比于碱性水溶液的优势在于,可以使原料中绝大部分硅铝组分转化为可溶的硅酸盐和铝酸盐,提高反应活性,然后通过水热反应合成得到晶相均匀,结晶度高的产品。另外,相较于传统的碱性水溶液合成方法,采用固体碱作为活化剂的碱熔-水热合成工艺可以提高产品的转化率,实现产品的高效制备。
本发明所述一种高炉渣基复合材料的制备方法,步骤二中,采用磷酸盐进行反应制备羟基磷灰石-沸石复合材料,相较于传统的磷酸活化法,由于不需要对过量的磷酸进行中和,本发明可以显著降低后续氢氧化钠的用量,且反应体系均为碱性环境,为羟基磷灰石-沸石复合材料制备提供了很好的反应条件。
本发明所述一种高炉渣基复合材料的制备方法,所述高炉渣优选炼钢生铁渣,基于高炉渣的组成及碱融活化处理,羟基磷灰石-沸石复合材料可以实现“一锅法”,相较于传统的分步制备,可提高生产效率。
本发明所述一种高炉渣基复合材料的制备方法,步骤二中,所述加入NaOH溶液充分混合的反应过程需要剧烈搅拌,以提高产品的分散性。
本发明采用上述技术方案后,主要有以下效果:
(1)本发明充分利用高炉渣自身组成特点,可以实现高炉渣中SiO2,CaO,Al2O3等主要成分的高效利用;且本发明是可在常压,80~100℃下进行,相比较在高压釜内以较高的温度(120-200℃)和高压下进行,具有明显的安全优势;
(2)本发明相较于传统强酸活化处理后在进行产品制备,本发明不涉及强酸活化处理,一方面,减少后续处理过程中碱的添加量,另一方面,不会导致高炉渣中重金属在强酸活化过程的潜在泄露,具有良好的环境友好性;
(3)本发明相较于传统强酸活化处理后在进行产品制备,首先将高炉渣中的难处理的硅铝质转变为可溶性的硅酸盐及偏铝酸盐,以提高反应活性,可以显著降低制备时间,传统强酸活化—碱溶水热反应,反应时间需要在3d以上,而本发明在6~10h反应后即可制备得到相应产品;
(4)发明所提出的方法对高炉渣进行处理,在80~100℃下反应6~10h即可制备得到羟基磷灰石-沸石复合材料,且每100g高炉渣可以制备86.56g羟基磷灰石-沸石复合材料,具有减量效率高、有用成分回收率高、工艺简单、条件温和等特点;
(5)本发明所制备的高炉渣基羟基磷灰石-沸石复合材料可广泛应用于水处理过程中,在室温下分别对50mg/L的Mn2+,NH4 +,HPO4 2-进行吸附处理,其吸附容量分别高达24.68~26.58mg/g,20.10~23.08mg/g和24.40~26.41mg/g,对于磷酸盐的吸附水平完全能够达到目前以传统强酸活化—碱溶水热反应所制备得到产品对磷酸盐的吸附能力,且本发明所制备的高炉渣基羟基磷灰石-沸石复合材料能够同时吸附铵盐,重金属,磷酸盐,且均有良好的吸附效果;
(6)本发明具有原料廉价,所需设备简单等特点,近一步降低了生产成本,利于推广利用,从而形成环保高效的高炉渣资源循环利用新工艺。
附图说明
图1为实施例1制备所得高炉渣基羟基磷灰石-沸石复合材料的SEM图谱;
图2为实施例1制备所得高炉渣基羟基磷灰石-沸石复合材料的XRD图谱;
图3为实施例1制备所得高炉渣基羟基磷灰石-沸石复合材料的元素分析图谱;
图4为实施例2制备所得高炉渣基羟基磷灰石-沸石复合材料的SEM图谱;
图5为实施例2制备所得高炉渣基羟基磷灰石-沸石复合材料的XRD图谱;
图6为实施例2制备所得高炉渣基羟基磷灰石-沸石复合材料的元素分析图谱;
图7为实施例3制备所得高炉渣基羟基磷灰石-沸石复合材料的SEM图谱;
图8为实施例3制备所得高炉渣基羟基磷灰石-沸石复合材料的XRD图谱;
图9为实施例3制备所得高炉渣基羟基磷灰石-沸石复合材料的元素分析图谱。
具体实施方式
本发明由下列实施例进一步说明,但不受这些实施例的限制,实施例中所有百分数除另有规定外均指质量百分数。
实施例1
高炉渣采集自江苏某钢铁股份有限公司,其主要成分含量为:SiO229.13%,CaO47.08%,Al2O3 20.59%,MgO 1.11%。高炉渣基羟基磷灰石-沸石复合材料的制备步骤如下:
(1)将高炉渣与氢氧化钠按质量比1:1.3均匀混合,在600℃下熔融60min后,得到熔融产物;
(2)控制反应体系Ca/P摩尔比为10:6的条件下,并将第(1)步所得的熔融产物转移到三口烧瓶中并加入30mL 2.0mol/L磷酸氢二钠溶液,搅拌均匀后,继续加入50mL 2.0mol/L NaOH溶液,于100℃下剧烈搅拌1h后,晶化6h;
(3)第(2)步中晶化完成后,将产品取出过滤,水洗滤饼至中性,80℃干燥3h,得到高炉渣基羟基磷灰石-沸石复合材料,制备所得高炉渣基羟基磷灰石-沸石复合材料的微观形貌、物相构成及元素分析分别如图1,图2,图3所示。并对其进行吸附容量测试,结果表明在室温下分别对50mg/L的Mn2+,NH4 +,HPO4 2-进行吸附处理,其吸附容量分别高达25.98mg/g,20.10mg/g和26.41mg/g。
实施例2
高炉渣与实施例1相同,高炉渣基羟基磷灰石-沸石复合材料的制备步骤如下:
(1)将高炉渣与氢氧化钠颗粒按质量比1:1.3均匀混合,在550℃下熔融60min后,得到熔融产物;
(2)控制反应体系Ca/P摩尔比为10:6的条件下,并将第(1)步所得的熔融产物转移到三口烧瓶中并加入30mL 2.0mol/L磷酸二氢钠溶液,搅拌均匀后,继续加入50mL 2.0mol/L NaOH溶液,于100℃下剧烈搅拌2h后,晶化8h;
(3)第(2)步中晶化完成后,将产品取出过滤,水洗滤饼至中性,80℃干燥3h,得到高炉渣基羟基磷灰石-沸石复合材料。制备所得高炉渣基羟基磷灰石-沸石复合材料的微观形貌、物相构成及元素分析分别如图4,图5,图6所示。并对其进行吸附容量测试,结果表明在室温下分别对50mg/L的Mn2+,NH4 +,HPO4 2-进行吸附处理,其吸附容量分别高达24.68mg/g,22.10mg/g和24.40mg/g。
实施例3
高炉渣与实施例1相同,高炉渣基羟基磷灰石-沸石复合材料的制备步骤如下:
(1)将高炉渣与氢氧化钠颗粒按质量比1:1.2均匀混合,在500℃下熔融120min后,得到熔融产物;
(2)控制反应体系Ca/P摩尔比为10:6的条件下,并将第(1)步所得的熔融产物转移到三口烧瓶中并加入30mL 2.0mol/L磷酸二氢钠溶液,搅拌均匀后,继续加入50mL 2.0mol/L NaOH溶液,于100℃下剧烈搅拌2h后,晶化6h;
(3)第(2)步中晶化完成后,将产品取出过滤,水洗滤饼至中性,80℃干燥3h,得到高炉渣基羟基磷灰石-沸石复合材料。制备所得高炉渣基羟基磷灰石-沸石复合材料的微观形貌、物相构成及元素分析分别如图7,图8,图9所示。并对其进行吸附容量测试,结果表明在室温下分别对50mg/L的Mn2+,NH4 +,HPO4 2-进行吸附处理,其吸附容量分别高达26.58mg/g,23.08mg/g和25.32mg/g。
以上实施方式仅用于说明本发明,而非对本发明的限制。尽管参照实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,对本发明的技术方案进行各种组合、修改或者等同替换,都不脱离本发明技术方案的精神和范围,均应涵盖在本发明的权利要求范围当中。
Claims (7)
1.一种高炉渣基复合材料的制备方法,其特征在于,所述方法包括:
步骤一:将高炉渣与碱性介质颗粒按质量比1:1.2~1:1.3均匀混合,在500~600℃下熔融60~120 min后,得到熔融产物;
步骤二:控制反应体系Ca/P摩尔比为10:6的条件下,并将步骤一所述熔融产物转移到反应容器中,并加入适量的2.0 mol/L磷酸盐溶液,搅拌均匀后,继续加入适量的2.0 mol/LNaOH 溶液,于100 ℃下剧烈搅拌1~2 h后,晶化6~8 h;
步骤三:将步骤二所述晶化产品取出过滤,水洗滤饼至中性,于干燥温度60~80℃下干燥1~3h后得到羟基磷灰石-沸石复合材料即高炉渣基复合材料。
2.根据权利要求1所述的方法,其特征在于,所述步骤一中,所述的碱性介质颗粒为氢氧化钠、氢氧化钾、碳酸氢钠、碳酸钠、碳酸氢钾、碳酸钾中的任意一种。
3.根据权利要求1所述的方法,其特征在于,所述步骤二中,所述磷酸盐溶液为磷酸二氢钾、磷酸氢二钾、磷酸二氢钠、磷酸氢二钠、磷酸钠、磷酸二氢钙、磷酸氢钙中的任意一种。
4.根据权利要求1所述的方法,其特征在于,所述高炉渣为炼钢生铁渣。
5.根据权利要求4所述的方法,其特征在于,所述高炉渣的主要成分含量为:SiO229.13%,CaO 47.08%,Al2O3 20.59%,MgO 1.11%。
6.一种水处理剂,其特征在于,包含权利要求1-5中任意一项所述方法制备的高炉渣基复合材料。
7.根据权利要求6所述的一种水处理剂,其特征在于,所述水处理剂应用于对铵盐,重金属,磷酸盐的吸附。
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