纳米颗粒作为稳泡剂泡沫分离酪蛋白的工艺

doi:10.16085/j.issn.1000-6613.2019-0963

摘要/Abstract

摘要：

为了增强乳制品废水中低浓度酪蛋白（casein，CS）的泡沫性能进而提高其泡沫分离效果，首先采用十二烷基二甲基甜菜碱（dodecyl dimethyl betaine，BS12）改性疏水二氧化硅纳米颗粒（silica nanoparticle，SNP），以制备接触角为61.6°±3.1°的部分疏水二氧化硅纳米颗粒（BS12-SNP），分别从静态和动态泡沫性能两个角度来研究BS12-SNP作为稳泡剂的功效。实验结果表明，BS12-SNP作为稳泡剂可以抑制泡沫排液和泡沫聚并，进而增强20.0～60.0mg/L酪蛋白的泡沫稳定性。与不添加BS12-SNP相比，添加BS12-SNP后的酪蛋白废水泡沫半衰期最大可提高6.5倍。泡沫分离实验表明，在BS12-SNP浓度50mg/L、气速250mL/min、装液量500mL的条件下，上述浓度范围内的酪蛋白回收率最高可达94.2%，此时富集比为12.3。本文开发了一种表面功能化纳米颗粒代替表面活性剂的泡沫分离工艺，实现了废水中酪蛋白的有效回收。

关键词: 二氧化硅, 纳米颗粒, 稳泡剂, 泡沫分离, 酪蛋白

Abstract:

In order to enhance the foaming properties of low concentration casein (CS) in dairy wastewater and then improve its performance of foam separation, dodecyl dimethyl betaine (BS12) was used to modify hydrophobic silica nanoparticle (SNP) to prepare a partially hydrophobic SNP (BS12-SNP) with a contact angle of 61.6°±3.1°. This paper studied the effect of BS12-SNP as a foam stabilizer from the static and dynamic foam properties. The results of experiments showed that BS12-SNP could act as a foam stabilizer to inhibit foam drainage and coalescence, thereby enhancing the foam stability of casein (20.0mg/L to 60.0mg/L). The half-life of CS with BS12-modified SNP could be increased by up to 6.5 times compared with that without BS12-SNP. Furthermore, the results of foam separation experiments showed that the maximum recovery percentage of casein at the above concentration range reached 94.2% and the enrichment ratio reached 12.3, under the conditions of the BS12-SNP concentration 50mg/L, air flow rate 250mL/min and liquid volume 500mL. A technology of foam separation with surface-functionalized nanoparticles instead of surfactant was developed and the efficient recovery of casein from its wastewater was realized.

Key words: silica, nanoparticle, foam stabilizer, foam separation, casein

中图分类号:

TQ028

李子薇,胡楠,杨松琴,吴兆亮. 纳米颗粒作为稳泡剂泡沫分离酪蛋白的工艺[J]. 化工进展, 2020, 39(3): 851-857.

Ziwei LI,Nan HU,Songqin YANG,Zhaoliang WU. Technology of foam separation of casein using nanoparticle as a foam stabilizer[J]. Chemical Industry and Engineering Progress, 2020, 39(3): 851-857.

图/表 11

表1 CS废水水质情况

参数	数值
pH	4.5～5.3
浓度/mg·L^-1	20.0～60.0
电导率/μS·cm^-1	16.2～16.8
颜色	透明
COD	266.0～520.0

图1 实验装置示意图1—空气压缩机；2—缓冲器；3—空气加湿瓶；4—转子流量计；5—液压阀；6—气体分布器；7—泡沫分离柱；8—泡沫收集器

图2 BS12- SNP浓度对泡沫高度H的影响

图3 BS12- SNP浓度对泡沫半衰期t1/2的影响

图4 疏水SNP的改性过程示意图

图5 CS和CS/BS12-SNP泡沫中的持液量与时间的关系

表2 泡沫形态随时间变化的示意图

废水	泡沫形态
废水	t=250s	t=500s	t=1000s	t=2000s
50.0mg/L CS
50.0mg/L CS+25.0mg/L BS12-SNP
50.0mg/L CS+50.0mg/L BS12-SNP
50.0mg/L CS+75.0mg/L BS12-SNP

图6 BS12-SNP对气泡直径随泡沫高度以及泡沫从柱内流出的持液量(εout)的影响

图7 BS12-SNP对不同浓度CS回收率和富集比的影响

图8 CS(30.0mg/L)+BS12-SNP(50.0mg/L)时表观气速对RCS、ECS和εout的影响

表3 CS回收率和富集比小结

废水	R_CS	E_CS
20.0mg/L CS	62.4%	44.2
30.0mg/L CS	77.1%	31.3
40.0mg/L CS	81.5%	21.9
50.0mg/L CS	86.1%	16.5
60.0mg/L CS	87.1%	13.4
20.0mg/L CS+50.0mg/L BS12-SNP	66.2%	40.8
30.0mg/L CS+50.0mg/L BS12-SNP	82.0%	29.6
40.0mg/L CS+50.0mg/L BS12-SNP	87.7%	20.5
50.0mg/L CS+50.0mg/L BS12-SNP	93.3%	15.2
60.0mg/L CS+50.0mg/L BS12-SNP	94.2%	12.3

参考文献 19

1	杨建英,沈玉如.人工食物链——凝聚沉淀法在乳品厂废水处理中的应用[J].中国乳品工业,1991(1):29-35.
	YANG Jianying,SHEN Yuru.Application of artificial food chain—Coagulation and precipitation method in wastewater treatment of dairy plants[J].China Dairy Industry,1991(1):29-35.
2	李宝宏.间歇式活性污泥法处理乳制品废水[J].科学技术与工程,2006,6(20):3376-3381.
	LI Baohong.Treatment of dairy wastewater by batch activated sludge process[J].Science Technology and Engineering,2006,6(20):3376-3381.
3	HOLT C,CARVER J A,ECROVD H,et al.Invited review: caseins and the casein micelle: their biological functions, structures, and behavior in foods [J].Journal of Dairy Science,2013,96(10):6127-6146.
4	BIAN H,PLANK J.Effect of heat treatment on the dispersion performance of casein superplasticizer used in dry-mix mortar [J].Cement and Concrete Research,2013,51:1-5.
5	HU Nan,LIU Wei,DING L L,et al.Removal of Methylene Blue from its aqueous solution by froth flotation: hydrophobic silica nanoparticle as a collector[J].Journal of Nanoparticle Research,2017,19(2):46.
6	CHEN Y C,PARLAR H.Enrichment behavior of immunoglobulin by foam fractionation using response surface methodology[J].Separation & Purification Technology,2013,107(107):102-108.
7	魏宣彪,刘桂敏,吴兆亮,等.pH对酪蛋白/十二烷基硫酸钠体系泡沫性能及泡沫分离酪蛋白的影响[J].高校化学工程学报,2010,24(6):949-953.
	WEI Xuanbiao,LIU Guimin,WU Zhaoliang,et al.Effect of pH on the foam properties of casein/sodium dodecyl sulfate system and foam separation of casein[J].Journal of Chemical Engineering of Chinese Universities,2010,24(6):949-953.
8	TIAN S,WU Z,LIU W,et al.Effective recovery of casein from its highly diluted solution by using a technology of foam fractionation coupled with isoelectric precipitation[J].Journal of Food Engineering,2018,216:72-80.
9	NAZARI MOGHADDAM R,BAHRAMIAN A,FAKHROUEIAN Z,et al.Comparative study of using nanoparticles for enhanced oil recovery: wettability alteration of carbonate rocks[J].Energy & Fuels,2015,29(4):2111-2119.
10	JIANG L,LI S,YU W,et al.Interfacial study on the interaction between hydrophobic nanoparticles and ionic surfactants[J].Colloids and Surfaces A: Physicochemical and Engineering Aspects,2016,488:20-27.
11	HU N,SHU T,WU Z,et al.BS12-assisted flotation for the intensification of SNPs separation from CMP wastewater using a novel flotation column[J].Journal of Hazardous Materials,2017,344:788-796.
12	HU Nan,WU Zhaoliang,JIN Lixue,et al.Nanoparticle as a novel foam controller for enhanced protein separation from sweet potato starch wastewater[J].Separation and Purification Technology,2019,209:392-400.
13	孙瑞娉,殷昊,卢珂,等.两级泡沫分离废水中大豆蛋白的工艺[J].农业工程学报,2010,26(11):374-378.
	SUN Ruiping,YIN Hao,LU Ke,et al.Process for separation of soybean protein from wastewater by two-stage foam[J].Transactions of the Chinese Society of Agricultural Engineering,2010,26(11):374-378.
14	LIU K,JIANG J,CUI Z,et al.pH-responsive pickering emulsions stabilized by silica nanoparticles in combination with a conventional zwitterionic surfactant[J].Langmuir the ACS Journal of Surfaces & Colloids,2017,33(9):2296.
15	YANG W,WANG T,FAN Z,et al.Foams stabilized byin situ-modified nanoparticles and anionic surfactants for enhanced oil recovery[J].Energy & Fuels,2017,31(5):4721-4730.
16	ARRIAGA L R,DRENCKHAN W,SALONEN A,et al.On the long-term stability of foams stabilised by mixtures of nano-particles and oppositely charged short chain surfactants[J].Soft Matter,2012,8(43):11085.
17	曲险峰,倪玲英,刘晓成,等.影响聚结效率因素实验研究[J].过滤与分离,2009,19(3):14-16.
	QU Xianfeng,NI Lingying,LIU Xiaocheng,et al.Experimental study on factors affecting coalescence efficiency[J].Filtration and Separation,2009,19(3):14-16.
18	ZHANG Z,WU Z,LIU G.Interfacial adsorption of methyl orange in liquid phase of foam fractionation using dodecyl dimethyl betaine as the collector[J].Journal of Industrial and Engineering Chemistry,2015,28:184-189.
19	YAN J,WU Z,WANG W.Separation of tea saponin by two-stage continuous foam fractionation[J].Separation Science and Technology,2012,47(16):2460-2466.

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