CN109422414B - 治理葡萄糖工业废水的环保工艺 - Google Patents
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Abstract
本发明属于环保技术领域,公开了治理葡萄糖工业废水的环保工艺,其包括如下步骤:将酵母菌种子液接种量接种到葡萄糖工业废水中,培养24‑48h,板框过滤收集菌体用作制备菌体蛋白,液体排出进入沉淀池,静置24‑36h,然后进入吸附净化池,添加吸附净化剂,搅拌20min,再进行吸附净化处理24‑48h,然后经过超滤膜过滤得透过液,进入生产用水系统再次使用。本发明工艺环保无污染,处理效果好,得到的回收水可作生产用水循环使用或用于清洗水用,节能减排,一举两得。
Description
技术领域
本发明属于环保技术领域,具体涉及治理葡萄糖工业废水的环保工艺。
背景技术
葡萄糖(Glucose)又称为玉米葡糖、玉蜀黍糖,简称为葡糖。英文另名:Dextrose,Cornsugar,Grapesugar,Bloodsugar,是自然界分布最广且最为重要的一种单糖,它是一种多羟基醛。纯净的葡萄糖为无色晶体,有甜味但甜味不如蔗糖(一般人无法尝到甜味),易溶于水,微溶于乙醇,不溶于乙醚。水溶液旋光向右,故属于“右旋糖”。葡萄糖在生物学领域具有重要地位,是活细胞的能量来源和新陈代谢中间产物,即生物的主要供能物质。植物可通过光合作用产生葡萄糖。在糖果制造业和医药领域有着广泛应用。葡萄糖一般以淀粉为原料,经淀粉调浆、液化、糖化、除渣、脱色、树脂吸附、结晶、分离、烘干等工序加工而成。它是食品加工、医药产品、工业发酵等行业的重要原料,具有很强的实用性。
然而,葡萄糖生产中,在结晶分离葡萄糖后,会存留大量的母液,这些母液干物浓度在50%左右,还原糖(DE值)含量在88%左右。由于该母液干物浓度低,极易发酵,存储期不能超过两天,加之其含水量50%左右,限制了远途运输,商品价值极低,而且成为新污染的可能又极大。母液回收重新结晶提取结晶葡萄糖,又会影响结晶葡萄糖的品质,不利用又会增加生产成本,造成极大的浪费。目前结晶葡萄糖生产企业中一部分将产生的母液返回糖化工序重新糖化、浓缩、结晶生产结晶葡萄糖,随着母液返回次数的增加,结晶葡萄糖的质量会大幅下降且保存过程中易结块,因此需定期外排母液;其余企业生产全糖粉,主要用于中低档食品的食品甜味剂、固体饮料及饼干中,但市场需求量不大且分布较散。申请人之前的专利技术CN104962547A公开了一种结晶葡萄糖清洁生产工艺,该工艺利用生物制剂对废水进行处理,效果较好,但是存在废水中的糖分没有得到有效利用,处理过的废水含有一些微生物产生的糖类以及蛋白等有机质,只能用于农业灌溉或肥料制备等,并不能循环回收重新利用到淀粉制备葡萄糖的工艺中。
发明内容
为了克服现有技术的不足,本发明提供了治理葡萄糖工业废水的环保工艺。本发明工艺处理废水效率高,可以重新循环使用,节省了水资源,并且避免了废水对环境的污染,一举两得。
本发明是通过如下技术方案来实现的:
治理葡萄糖工业废水的环保工艺,其包括如下步骤:
将酵母菌种子液按照6-8%的接种量接种到葡萄糖工业废水中,培养24-48h,板框过滤收集菌体用作制备菌体蛋白,液体排出进入沉淀池,静置24-36h,然后进入吸附净化池,按照每立方米液体添加10-20g的量添加吸附净化剂,搅拌20min,再进行吸附净化处理24-48h,然后经过超滤膜过滤得透过液,进入生产用水系统再次使用。
进一步地,所述酵母菌种子液的浓度为1×108cfu/ml。
进一步地,所述沉淀池的底部填料为100cm厚度的河沙,河沙的粒径为1-2mm。
进一步地,所述超滤膜的截留分子量为200Da,超滤温度为25-30℃,工作压力:进压为5bar,出压为3bar。
进一步地,所述搅拌的转速为300rpm。
进一步地,所述吸附净化剂按照每立方米液体添加10-20g的量来添加。
进一步地,所述吸附净化剂按照如下工艺制备而得:
1)往浓度为7wt%聚乙烯醇水溶液中加入氯化铝和玻璃纤维,搅拌均匀,然后80℃热处理60min,冷却至室温,得到组分a;所述聚乙烯醇水溶液、氯化铝以及玻璃纤维的质量比为10:3:1;
2)往凹凸棒土中加入2倍重量的浓度为5M的盐酸溶液,超声波振荡30min,然后添加纳米氧化铝以及钛酸酯偶联剂,200rpm搅拌10min,再静置60min,即得组分b;其中,凹凸棒土、纳米氧化铝以及钛酸酯偶联剂的质量比为5:1:1;超声波功率为2000w;
3)将三氯化铁和草炭土添加到水中,加热搅拌至干,然后放入烘干箱中于80℃干燥30min,即得组分c;所述三氯化铁、草炭土以及水的质量比为1:2:4;
4)将组分a、组分b以及组分c按照4:2:1的质量比投入到搅拌器中,1000rpm搅拌3min,得到混合物料,再将混合物料与聚苯乙烯微球按照1:1的质量比添加到造粒机中,得到颗粒物,然后置于90℃的烘箱中干燥20min,再投入到烧结炉中进行烧结,烧结温度700℃,保温30min,取出,自然冷却至室温,即得。
本发明主要包括但是并不限于以下的有益效果:
本发明结晶葡萄糖清洁生产工艺简单可行,节能减排,废水处理效果好,符合环保标准;
本发明工艺采用栅栏和沉淀池用于去除由淀粉、蛋白质、纤维以及树脂等组成的絮凝物;
本发明工艺具有投资费用小,操作维护简单,能使出水稳定达标且废水得到资源化利用的优点,可以重新循环使用,节省了水资源,并且避免了废水对环境的污染,一举两得;
本发明着重对吸附净化剂进行了改进,其中以聚乙烯醇作为碳源,利用聚乙烯醇分子链上的羟基可同铝离子发生强的相互作用,使得铝离子和玻璃纤维在最终的碳基复合材料的表面和内层均相分布,粗糙度和比表面积大,提高了交换容量;
凹凸棒土具备介于链状结构和层状结构之间的中间结构,没交联时强度低、易拉断,且没有弹性,吸附和粘结性低,本发明通过酸化和偶联处理,纳米氧化铝材料可以较好的偶联附着到凹凸棒土的层间空隙,相互交联成网状结构,从而增加其比表面积和粘结度,提高吸附无机小分子性能;
本发明吸附净化剂中对草炭土进行了改性,表面变得较为粗糙,增大了比表面积,再经与三氯化铁掺杂后,团聚在其表面,提高了吸附氨氮等有机污染物的能力,使吸附剂的活性保持稳定继续发挥吸附作用;
本发明利用造孔剂制备成大孔径颗粒吸附剂,比表面积大,强度高,不会破裂,还可以经过煅烧工艺后再次重复利用,有效地避免了材料浪费,给企业节约了成本。
具体实施方式
为了使本技术领域的人员更好地理解本申请中的技术方案,下面将结合本申请具体实施例,对本发明进行更加清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都应当属于本发明保护的范围。
实施例1
治理葡萄糖工业废水的环保工艺,其包括如下步骤:
玉米淀粉制备的糖液用活性炭脱色30min,透光≥98%;所得料液再经过离子交换,将料液中的盐份、色素和异味物质去除,使糖液得到彻底净化,要求进料温度45-50℃,出料pH3.5-5.0,透光率≥98%;
再加入1-2wt%的珍珠岩助滤剂,搅拌脱色30分钟,然后过滤;所得滤液蒸发至浓缩70-72%,进入结晶机,助晶罐温度50±1℃,混合罐温度44-46℃,放料收率53~58%,降温速率1℃/3h;结晶机出料后采用高速离心机,将结晶体和液体分离,要求水份≤14%,所得结晶体烘干后作为成品出售,所得液体即为葡萄糖工业废水;
利用酵母菌CGMCC NO.2959种子液(浓度为1×108cfu/ml)按照6%的接种量接种到葡萄糖工业废水中,培养24h,板框过滤收集菌体用作制备菌体蛋白,液体排出进入沉淀池,静置36h,其中,沉淀池的底部填料为100cm厚度的河沙,河沙的粒径为1mm,可对一些絮凝杂质进行初步吸附和沉淀;然后进入吸附净化池,按照每立方米液体添加12g的量添加吸附净化剂,以300rpm的转速搅拌20min,然后停止搅拌,吸附处理24h,再经过超滤膜过滤去除糖、盐以及其他细小杂分子,得透过液,进入生产用水系统再次使用。所述超滤膜的截留分子量为200Da,超滤温度为25-30℃,工作压力:进压为5bar,出压为3bar;
所述吸附净化剂按照如下工艺制备而得:
1)往浓度为7wt%聚乙烯醇水溶液中加入氯化铝和玻璃纤维,搅拌均匀,然后80℃热处理60min,冷却至室温,得到组分a;所述聚乙烯醇水溶液、氯化铝以及玻璃纤维的质量比为10:3:1;
2)往凹凸棒土中加入2倍重量的浓度为5M的盐酸溶液,超声波振荡30min,然后添加纳米氧化铝以及钛酸酯偶联剂,200rpm搅拌10min,再静置60min,即得组分b;其中,凹凸棒土、纳米氧化铝以及钛酸酯偶联剂的质量比为5:1:1;超声波功率为2000w;
3)将三氯化铁和草炭土添加到水中,加热搅拌至干,然后放入烘干箱中于80℃干燥30min,即得组分c;所述三氯化铁、草炭土以及水的质量比为1:2:4;
4)将组分a、组分b以及组分c按照4:2:1的质量比投入到搅拌器中,1000rpm搅拌3min,得到混合物料,再将混合物料与聚苯乙烯微球按照1:1的质量比添加到造粒机中,得到颗粒物,然后置于90℃的烘箱中干燥20min,再投入到烧结炉中进行烧结,烧结温度700℃,保温30min,取出,自然冷却至室温,制得粒径为2mm的颗粒物吸附剂。
实施例2
治理葡萄糖工业废水的环保工艺,其包括如下步骤:
玉米淀粉制备的糖液用活性炭脱色30min,透光≥98%;所得料液再经过离子交换,将料液中的盐份、色素和异味物质去除,使糖液得到彻底净化,要求进料温度45-50℃,出料PH3.5-5.0,透光率≥98%;
再加入1-2wt%的珍珠岩助滤剂,搅拌脱色30分钟,然后过滤;所得滤液蒸发至浓缩70-72%,进入结晶机,助晶罐温度50±1℃,混合罐温度44-46℃,放料收率53~58%,降温速率1℃/3h;结晶机出料后采用高速离心机,将结晶体和液体分离,要求水份≤14%,所得结晶体烘干后作为成品出售,所得分离液体即为葡萄糖工业废水;
利用酵母菌CCTCC NO.M208110种子液(浓度为1×108cfu/ml)按照8%的接种量接种到葡萄糖工业废水中,培养36h,板框过滤收集菌体用作制备菌体蛋白,液体排出进入沉淀池,静置24h,其中,沉淀池的底部填料为100cm厚度的河沙,河沙的粒径为1mm,可对一些絮凝杂质进行初步吸附和沉淀;然后进入吸附净化池,按照每立方米液体添加10-20g的量添加吸附净化剂,以300rpm的转速搅拌20min,然后停止搅拌,吸附处理24h,再经过超滤膜过滤去除糖、盐以及其他细小杂分子,得透过液,最后进入玉米淀粉加工用水系统进行再次使用。所述超滤膜的截留分子量为200Da,超滤温度为30℃,工作压力:进压为5bar,出压为3bar;
所述吸附净化剂按照如下工艺制备而得:
1)往浓度为7wt%聚乙烯醇水溶液中加入氯化铝和玻璃纤维,搅拌均匀,然后80℃热处理60min,冷却至室温,得到组分a;所述聚乙烯醇水溶液、氯化铝以及玻璃纤维的质量比为10:3:1;
2)往凹凸棒土中加入2倍重量的浓度为5M的盐酸溶液,超声波振荡30min,然后添加纳米氧化铝以及钛酸酯偶联剂,200rpm搅拌10min,再静置60min,即得组分b;其中,凹凸棒土、纳米氧化铝以及钛酸酯偶联剂的质量比为5:1:1;超声波功率为2000w;
3)将三氯化铁和草炭土添加到水中,加热搅拌至干,然后放入烘干箱中于80℃干燥30min,即得组分c;所述三氯化铁、草炭土以及水的质量比为1:2:4;
4)将组分a、组分b以及组分c按照4:2:1的质量比投入到搅拌器中,1000rpm搅拌3min,得到混合物料,再将混合物料与聚苯乙烯微球按照1:1的质量比添加到造粒机中,得到颗粒物,然后置于90℃的烘箱中干燥20min,再投入到烧结炉中进行烧结,烧结温度700℃,保温30min,取出,自然冷却至室温,制得粒径为2mm的颗粒物吸附剂。
实施例3
本发明工艺处理葡萄糖工业废水效果实例:
取阜丰葡萄糖生产车间的工业废水,经过栅栏进入沉淀池,对沉淀池的废水进行检测,记为处理前的废水指标;以实施例1为实验组,对照组1为:采用氯化铝吸附剂,其余同实施例1;对照组2为:采用硅藻土作为吸附剂,其余同实施例1;对照组3:采用活性炭作为吸附剂,其余同实施例1。具体检测结果见表1:
表1
处理前 | 对照组1 | 对照组2 | 对照组3 | 实验组 | |
COD (mg/L) | 1651 | 71.8 | 86.4 | 59.1 | 10.5 |
总固形物 (mg/L) | 3759 | 106.5 | 79.3 | 60.2 | 9.8 |
NH3-N (mg/L) | 136 | 18.5 | 11.2 | 16.9 | 1.7 |
硫化物 (mg/L) | 177 | 29.3 | 30.5 | 19.4 | 2.1 |
总磷 (mg/L) | 38 | 9.5 | 7.7 | 5.1 | 1.3 |
氯化物(mg/L) | 24 | 2.2 | 1.7 | 3.9 | 0.6 |
结论:本发明工艺处理效果好,吸附剂吸附污染物效果明显优于现有技术常用吸附剂,得到的回收水可作生产用水循环使用或用于清洗水用,节能减排,一举两得。
实施例4
本发明吸附剂性能指标测定:
以常用活性炭大颗粒吸附剂样品作为对照组,以实施例1制备的吸附净化剂作为实验组,检测了各组别的吸附剂各项指标参数,具体见表2:
表2
组别 | 粒径mm | 平均孔径nm | 孔容m<sup>3</sup> g<sup>-1</sup> | 比表面积m<sup>2</sup> g<sup>-1</sup> | 可使用天数 |
实验组 | 2 | 8.3 | 0.32 | 379 | 19 |
对照组 | 2 | 48.6 | 0.07 | 106 | 8 |
结论:本发明制备的吸附剂在平均孔径、孔容以及比表面积等多个指标均大大优于常用活性炭吸附剂,提示本发明吸附剂具备更佳的吸附效果。
实施例5
本发明吸附净化剂的再生工艺,包括如下步骤:将使用后的吸附净化剂置于350-400℃煅烧10min,降至室温,然后去除表面吸附物,用清水洗净,烘干,即完成了吸附净化剂的再生。
虽然,上文中已经用一般性说明及具体实施方式对本案作了详尽的说明,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所作的修改或改进,均属于本发明要求保护的范围。
Claims (4)
1.治理葡萄糖工业废水的环保工艺,其包括如下步骤:
将酵母菌种子液按照6-8%的接种量接种到葡萄糖工业废水中,培养24-48h,板框过滤收集菌体用作制备菌体蛋白,液体排出进入沉淀池,静置24-36h,然后进入吸附净化池,按照每立方米液体添加10-20g的量添加吸附净化剂,搅拌20min,再进行吸附净化处理24-48h,然后经过超滤膜过滤得透过液,进入生产用水系统再次使用;
所述吸附净化剂按照如下工艺制备而得:
1)往浓度为7wt%聚乙烯醇水溶液中加入氯化铝和玻璃纤维,搅拌均匀,然后80℃热处理60min,冷却至室温,得到组分a;所述聚乙烯醇水溶液、氯化铝以及玻璃纤维的质量比为10:3:1;
2)往凹凸棒土中加入2倍重量的浓度为5M的盐酸溶液,超声波振荡30min,然后添加纳米氧化铝以及钛酸酯偶联剂,200rpm搅拌10min,再静置60min,即得组分b;其中,凹凸棒土、纳米氧化铝以及钛酸酯偶联剂的质量比为5:1:1;超声波功率为2000W;
3)将三氯化铁和草炭土添加到水中,加热搅拌至干,然后放入烘干箱中于80℃干燥30min,即得组分c;所述三氯化铁、草炭土以及水的质量比为1:2:4;
4)将组分a、组分b以及组分c按照4:2:1的质量比投入到搅拌器中,1000rpm搅拌3min,得到混合物料,再将混合物料与聚苯乙烯微球按照1:1的质量比添加到造粒机中,得到颗粒物,然后置于90℃的烘箱中干燥20min,再投入到烧结炉中进行烧结,烧结温度700℃,保温30min,取出,自然冷却至室温,即得。
2.根据权利要求1所述的环保工艺,其特征在于,所述酵母菌种子液的浓度为1×108cfu/mL。
3.根据权利要求1所述的环保工艺,其特征在于,所述沉淀池的底部填料为100cm厚度的河沙,河沙的粒径为1-2mm。
4.根据权利要求1所述的环保工艺,其特征在于,所述超滤膜的截留分子量为200Da,超滤温度为25-30℃,工作压力:进压为5bar,出压为3bar。
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