CN114772986A - 一种生活垃圾焚烧飞灰提质并制备地聚合物的方法 - Google Patents
一种生活垃圾焚烧飞灰提质并制备地聚合物的方法 Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
- C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
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Abstract
本发明提出了一种生活垃圾焚烧飞灰提质并制备地聚合物的方法。工艺流程见图示,包括两次飞灰水洗、水洗废水回收利用和制备地聚合物浆料,其中重金属处理简单且得到了有效固定。所述两级飞灰水洗工艺,一级飞灰水洗在低液固比条件下,去除Na、K等可溶性氯盐,实现定向除盐;利用Na2SO4对一级水洗废水进行脱钙,得到杂盐水和石膏产品;二级飞灰水洗提高液固比同时定量添加Na2SO4,将焚烧飞灰在中Ca氧化物转化为Ca2SO4,同时过滤废水具有一定碱性,回收利用进行无害化处理。经两级水洗处理干燥后的焚烧飞灰研磨成粉,可作为地聚合物制备材料。本方法相较于热法处理焚烧飞灰能耗低,无二次污染,有效固定重金属,整个工艺过程实现净零排放,可实现焚烧飞灰资源化利用。
Description
技术领域
本发明属于地聚合物材料技术领域,特别涉及一种生活垃圾焚烧飞灰提质并制备地聚合物的方法。
背景技术
地聚合物是一种通过硅铝酸盐材料和硅酸盐溶液或高溶度碱金属氢氧化物反应,生成的一种由硅氧四面体和铝氧四面体合成的无定型三维网状结构的碱铝硅酸盐胶凝材料,属于无机聚合物。合成地聚合物的原材料来源于粉煤灰,矿渣等工业废弃物,与传统的无机硅酸盐胶凝材料相比,具有节约能源,同时也具有降低CO2排放的优势。地聚合物具有很多优异的特性,包括低收缩率,慢速或快速凝固,耐火性,低导热性和耐酸碱腐蚀等。此外,地聚合物可以完全避免普通硅酸盐水泥因为金属迁移与骨料反应从而引起的碱集料反应,具有良好的耐久性能。但经国内外研究发现,地聚合物后期的强度呈现下降的趋势,而且抗渗性也得到了不同程度地降低。
焚烧飞灰是在垃圾焚烧技术产生的一种从电除尘器收集的烟道工业固废,而且其主要成分与粉煤灰相似,都由Al2O3,SiO2和CaO等有毒化合物构成。飞灰中含有大量的钙化合物,主要是燃烧炉尾部喷射石灰石吸附硫化物,其中有大部分游离的氧化钙,氢氧化钙的等。焚烧飞灰粒径小,且含有部分氧化铝和二氧化硅,可用作建筑材料,同时焚烧飞灰中有一定的硫酸钙,在地聚合物的制备中,焚烧飞灰显现了较高的活性。而且焚烧飞灰中的硫酸钙在地聚合物合成过程中,能够提升胶凝材料的早期硬化,使得水化产物和缩聚产物更加紧密结合,因而胶凝材料体系硬化后体系结构更加致密,从而使得整体内部孔隙率下降。
鉴于垃圾焚烧飞灰制备地聚合物浆料具有较高的经济、社会和环境效益,可产出具有价值的产品、具备改善环境的作用、低能耗进程、消耗大量废弃物、副产物及飞灰利用率较高等优点,可进一步推广应用。整个工艺过程无三废排放,不仅实现了工业固废焚烧飞灰的无害化安全循环利用,而且为建材行业提供了新的途径。
发明内容
针对目前焚烧飞灰危害大且处理量巨大,本发明目的利用危险固废焚烧飞灰进行资源化利用,实现净零排放。本发明所制得的地聚合物材料具有强度高,有效固定重金属,耐腐蚀,环境友好等。为实现上述目的,本发明采用以下技术方案:
包括以下几个步骤:
(1)称取焚烧飞灰原料和水,置入一级飞灰水洗系统,之后送入一级飞灰脱水系统,得到一级飞灰滤饼和高盐废水;
(2)将步骤(1)中的一级飞灰滤饼送入二级飞灰水洗系统,之后送入二级飞灰脱水系统,得到二级飞灰滤饼和废碱液;
(3)将步骤(1)中的高盐废水送入脱钙池,经过滤池得到杂盐水和石膏产品;
(4)将步骤(2)的二级飞灰滤饼进行干燥脱水,得到干灰,混合偏高岭土或粉煤灰送入研磨系统;添加水玻璃和氢氧化钠至步骤(2)的废碱液,制取规定模数的碱激发剂溶液模数为1.2—1.6;
(5)将步骤(3)中的混合干灰和碱激发剂混合搅拌,同时添加体稳剂和粗骨料,得到地聚合物浆料。
进一步,所述焚烧飞灰中SiO2为10—20wt%,Al2O3为5—12wt%,CaO为35—48wt%,飞灰粒径小于80μm;优选的:偏高岭土中SiO2为54—55%,Al2O3为43—44%,细度为1250目。
进一步,所述一级飞灰水洗液固比小于2.5,一级飞灰脱水所得滤饼含水率40%;二级飞灰水洗液固比2.5—4L/kg,二级飞灰脱水所得滤饼含水率40%。
进一步,所述步骤(3)脱钙池测定脱钙池溶解性钙离子摩尔浓度,1:1摩尔比添加硫酸钠,所得杂盐水和含水率30%的石膏产品;
进一步,所述(4)所得废碱液,外加水玻璃和固体氢氧化钠制取规定碱激发剂模数为1.2—1.6。
进一步,所述步骤(4)中二级飞灰滤饼干燥后含水率<2%,干燥温度100℃,时间2h,将干燥后飞灰和偏高岭土干重比为2—4:6—8混合研磨。
进一步,所述步骤(5)碱激发剂和混合干灰添加比例为0.35—0.5,体稳剂添加量2—3wt%,优选的体稳剂为聚羧酸减水剂、萘系减水剂或三聚氰胺减水剂中的一种或多种。
本发明所述的一种生活垃圾焚烧飞灰提质并制备地聚合物的方法,将焚烧飞灰进行两次水洗,一级飞灰水洗使用低液固比,去除钠、钾等氯盐,二级飞灰水洗系统所得滤饼和滤水皆可回收利用,然后再进行地聚合物浆料的制备,最终的产物具有一定的抗压强度,且重金属溶出率低;本方法不仅可以处理大宗危废,同时资源化利用,减少危废对环境的污染;本发明的地聚合物浆料后期强度增强明显,实际应用过程中耐久性能较好。
附图说明:
图1为本发明的工艺流程示意图
具体实施方案:
以下结合具体实施例对本发明做进一步说明,但发明内容不限于这些具体实例。
实施例1
称取20份焚烧飞灰送入一级飞灰水洗系统,液固比设定为2.5L/kg,一级飞灰水洗结束后过滤分离;将一级水洗滤液测定溶解性钙离子摩尔浓度,1:1摩尔比添加硫酸钠,后经过滤分离获得杂盐水和石膏产品;将一级水洗含水率40%的滤饼送入二级飞灰水洗系统,液固比设定为3L/kg,同时测定溶解性钙离子摩尔浓度,1:1摩尔比添加硫酸钠,二级飞灰水洗结束过滤分离;将二级飞灰水洗滤液外加水玻璃和氢氧化钠制备碱激发剂,模数为1.3;将二级飞灰滤饼进行干燥,温度100℃,时间2h,将干燥后飞灰和偏高岭土干重比为4:6混合研磨;配制体稳剂(2wt%);将配制的碱激发剂和混合干灰比例为0.45搅拌混合,同时添加体稳剂,将获得的聚合物浆料注模成型,标准养护28d后测试聚合物块体抗压强度为58Mpa。
实施例2
称取40份焚烧飞灰送入一级飞灰水洗系统,液固比设定为2.5L/kg,一级水洗结束过滤分离;将一级水洗滤液测定溶解性钙离子摩尔浓度,1:1摩尔比添加硫酸钠,后经过滤分离获得工业杂盐水和石膏产品;将一级水洗含水率15%的滤饼送入二级飞灰水洗系统,液固比设定为4L/kg,同时测定溶解性钙离子摩尔浓度,1:1摩尔比添加硫酸钠,二级飞灰水洗结束过滤分离;将二级飞灰水洗滤液外加水玻璃和固体氢氧化钠制备碱激发剂,模数为1.5;将二级飞灰滤饼进行干燥,温度100℃,时间2h,将干燥后飞灰和偏高岭土干重比为3:7混合研磨;配制体稳剂(2wt%),其中体稳剂组分(铝灰30-45%,聚羧酸减水剂55-70%);将配制的碱激发剂和混合干灰比例为0.45搅拌混合,同时添加体稳剂,将获得的聚合物浆料注模成型,标准养护28d后测试聚合物块体抗压强度为41Mpa。
对比例3
称取40份焚烧飞灰混合60份偏高岭土,使用水玻璃和固体氢氧化钠配制模数为1.3的碱激发剂,配制体稳剂(2wt%),其中体稳剂组分(铝灰30-45%,聚羧酸减水剂55-70%),将配制的碱激发剂和混合干灰比例为0.45搅拌混合,同时添加体稳剂,将获得的聚合物浆料注模成型,标准养护28d后测试聚合物块体抗压强度为29Mpa。
由此可见,未经过飞灰水洗提质制作地聚合物,抗压强度下降严重,经过飞灰水洗提质工艺制备地聚合物浆料具有较高的经济、社会和环境效益,可产出具有价值的产品、具备改善环境的作用、低能耗进程、消耗大量废弃物、副产物及飞灰利用率较高等优点。
Claims (7)
1.一种生活垃圾焚烧飞灰提质并制备地聚合物的方法,其特征在于,包括以下步骤:
(1)将焚烧飞灰和水加入一级飞灰水洗系统,进行低液固比水洗,然后送入一级飞灰脱水系统,得到一级飞灰滤饼和高盐废水;
(2)将步骤(1)中的一级飞灰滤饼和硫酸钠以及水送入二级飞灰水洗系统,进行飞灰改性提质,然后送入二级飞灰脱水系统,得到二级飞灰滤饼和废碱液;
(3)将步骤(1)中的高盐废水和硫酸钠送入脱钙池脱钙,然后送入过滤池脱水,得到杂盐水和石膏产品;
(4)将步骤(2)的二级飞灰滤饼进行干燥脱水,得到干灰,混合偏高岭土或粉煤灰送入研磨系统,得到混合粉体料;
(5)添加硅酸钠和氢氧化钠至步骤(2)的废碱液中,经静置得到碱激发剂溶液;
(6)将步骤(3)中的混合粉料和碱激发剂溶液混合搅拌,同时添加体稳剂,得到地聚合物浆料。
2.根据权利要求1所述的一种生活垃圾焚烧飞灰提质并制备地聚合物的方法,其特征在于,所述步骤(1)中,一级飞灰水洗系统的液固比低于2.5L/kg,一级飞灰脱水系统所得的滤饼含水率低于40%,氯化钠和氯化钾溶出率为78%—92%。
3.根据权利要求1所述的一种生活垃圾焚烧飞灰提质并制备地聚合物的方法,其特征在于,所述步骤(2)中,二级飞灰水洗系统的液固比为2.5—4L/kg,水洗过程中添加硫酸钠对飞灰进行改性提质,测定溶解性钙离子摩尔浓度,1:1摩尔比添加硫酸钠,二级飞灰脱水所得滤饼含水率低于40%,二级飞灰废水pH为11—13。
4.根据权利要求1所述的一种生活垃圾焚烧飞灰提质并制备地聚合物的方法,其特征在于,所述步骤(3)中,测定脱钙池溶解性钙离子摩尔浓度,1:1摩尔比添加硫酸钠,经过滤所得杂盐水和含水率30%的石膏产品。
5.根据权利要求1所述的一种生活垃圾焚烧飞灰提质并制备地聚合物的方法,其特征在于,所述步骤(4)中,二级飞灰滤饼干燥后含水率低于<2%,所获得的粉料重量百分比为,偏高岭土或粉煤灰质量为60%—80%,干灰质量为40%—20%。
6.根据权利要求1所述的一种生活垃圾焚烧飞灰提质并制备地聚合物的方法,其特征在于,所述步骤(5)中,废碱液的碱性浓度为0.003—0.0045mol/L,硅酸钠和固体氢氧化钠添加至废碱液后得到的碱激发剂溶液模数(SiO2/Na2O摩尔比)为1.2—1.6,静置陈化18—36h后使用。
7.根据权利要求1所述的一种生活垃圾焚烧飞灰提质并制备地聚合物的方法,其特征在于,所述步骤(6)中,碱激发剂溶液和混合粉料质量添加比例为0.35—0.5,体稳剂添加量为混合粉料总质量的1—3%,体稳剂为聚羧酸减水剂、萘系减水剂或三聚氰胺减水剂中的一种或多种。
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CN115646986A (zh) * | 2022-10-28 | 2023-01-31 | 深圳大学 | 一种处理城市固体废物焚烧飞灰中二噁英的方法 |
CN116003009A (zh) * | 2022-12-28 | 2023-04-25 | 长安大学 | 一种用于路基改善层的飞灰基地聚合物及其制备方法 |
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