膨润土提纯、活化与联产白炭黑工艺技术研究
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摘要
膨润土是一种重要的非金属矿物,在很多工业领域中,被广泛应用。我国膨润土资源十分丰富,但我国利用其生产的主要产品仍处在初级加工阶段。膨润土活化、联产白炭黑不仅可以生产高附加值产品,而且可以满足高档产品日益增长的需求,进而高效利用膨润土资源。
本论文以辽西某膨润土为原料,深入研究活性白土制备机理、制定较佳的工艺流程,试验研究提纯、活化、制备白炭黑过程的各项工艺技术参数,制得了高效活性白土、白炭黑,同时循环利用废酸,确定最佳工艺参数。
试验表明:膨润土原矿经过钠化、分散提纯后,蒙脱石含量由70.00 %提高至84.67 %。
通过单因素探索性试验和正交试验确定了湿法活化制备活性白土的最佳工艺条件为:酸土比20 %、活化时间4 h、活化温度90℃、液固比4:1,性能测试结果为脱色率99.75 %、活性度223.1 mmol/100g、游离酸0.13 %,所测指标优于HG/T2569-94行业标准。
试验研究非金属矿离解法制备白炭黑,通过单因素试验确定了最佳工艺条件:酸土比66 %、酸溶时间3 h、酸溶温度100℃、酸溶液固比4:1、碱土比为17 %、碱溶时间3 h、碱溶温度100℃、碱溶液固比4:1、电解质加入量为1.5 %、无水乙醇加入量为10 %、中和反应温度80℃、pH=8、陈化时间30 min、陈化温度80℃、醇洗置换。性能测试结果为邻苯二甲酸二丁酯吸收值2.05 ml/g、水悬浮液pH为6.8、加热减量4.0 %,SiO2含量90.94 %,所测指标均达到HG/T3061-1999行业标准。
基于“循环利用活性白土和白炭黑的废酸液,降低酸耗,节约水资源”的工艺技术试验研究,制得了不同质量的活性白土,性能测试结果分别为脱色率97.37 %、活性度200.7 mmol/100g;脱色率93.65 %、活性度188.4 mmol/100g,所测指标都达到了HG/T2569-94行业标准,此技术的应用具有良好的社会效益、经济效益和环境效益。
Bentonite is an important non-metallic mineral,it is widely applied to many industrial fields. In our country,bentonite resource is quite abundant, but its master production is still in primary phase. Bentonite is activated and used for producing white carbon at the same time, which can not only produce goods with high added value but also meet the growing demand for the upper-end products, sequentially, utilize bentonite resource high-efficiently.
Bentonite in western Liaoning Province is chosen as raw material, this paper lucubrates the mechanism of preparation, draws up the better technological process, studies every technical parameter in the processes which include purification, activation and preparation of white carbon, obtains high-efficient activated clay and white carbon, at the same time, recycles acid pickle and confirms the optimal technical parameters.
After the bentonite is purified by means of sodium modification and dispersion, the experiment shows that the montmorillonite content is rising from 70.00% to 84.67%.
By means of single factor exploratory research and orthogonal test, the experiment confirms the optimal technological conditions in producing activated clay by wet method. Acid-clay ratio is 20%, activation time is 4h, activation temperature is 90℃, solid-liquid ratio is 4:1. According to the conditions, the production is tested. The performance testing results are as following. The decolouring ratio is 99.75%, the activity is 223.1mmol/100g, the free acid is 0.13%. These indicators precede the requests of the HG/T2569-94 industry standard.
The experiment studies preparation of white carbon by means of non-metallic minerals separation method. The optimal technological conditions which base on the single factor method are as following. Acid-clay ratio is 66%, acid dissolution time is 3h, acid dissolution temperature is 100℃, acid dissolution solid-liquid ratio is 4:1, alkali-clay ratio is 17%, alkali dissolution time is 3h, alkali dissolution temperature is 100℃, alkali dissolution solid-liquid ratio is 4:1, proportion of adding electrolyte is 1.5%, proportion of adding absolute ethyl alcohol is 10%, neutralization temperature is 80℃, pH=8, aging time is 30 min, aging temperature is 80℃, absolute ethyl alcohol is adopted to rinse the products in permutation. According to the conditions, the production is tested. The performance testing results are as following. The absorption value of Dibutyl Phthalate is 2.05ml/g, pH of the suspending liquid is 6.8, the heating loss is 4.0%. SiO2 content reaches 90.94%. These indicators are all in keeping with the requests of the HG/T3061-1999 industry standard.
Being based on the technical experimental research of recycling acid pickle from preparation of activated clay and white carbon, reducing acid dosage and saving water resource, the activated clay of different quality is obtained in the experiment. The production performance testing results are as following. The decolouring ratio is 97.37% and 93.65%, respectively, the activity is 200.7mmol/100g and 188.4mmol/100g. These indicators are all in keeping with the requests of the HG/T2569-94 industry standard. The application of technology will make favorable social, economic and environmental benefit.
本论文以辽西某膨润土为原料,深入研究活性白土制备机理、制定较佳的工艺流程,试验研究提纯、活化、制备白炭黑过程的各项工艺技术参数,制得了高效活性白土、白炭黑,同时循环利用废酸,确定最佳工艺参数。
试验表明:膨润土原矿经过钠化、分散提纯后,蒙脱石含量由70.00 %提高至84.67 %。
通过单因素探索性试验和正交试验确定了湿法活化制备活性白土的最佳工艺条件为:酸土比20 %、活化时间4 h、活化温度90℃、液固比4:1,性能测试结果为脱色率99.75 %、活性度223.1 mmol/100g、游离酸0.13 %,所测指标优于HG/T2569-94行业标准。
试验研究非金属矿离解法制备白炭黑,通过单因素试验确定了最佳工艺条件:酸土比66 %、酸溶时间3 h、酸溶温度100℃、酸溶液固比4:1、碱土比为17 %、碱溶时间3 h、碱溶温度100℃、碱溶液固比4:1、电解质加入量为1.5 %、无水乙醇加入量为10 %、中和反应温度80℃、pH=8、陈化时间30 min、陈化温度80℃、醇洗置换。性能测试结果为邻苯二甲酸二丁酯吸收值2.05 ml/g、水悬浮液pH为6.8、加热减量4.0 %,SiO2含量90.94 %,所测指标均达到HG/T3061-1999行业标准。
基于“循环利用活性白土和白炭黑的废酸液,降低酸耗,节约水资源”的工艺技术试验研究,制得了不同质量的活性白土,性能测试结果分别为脱色率97.37 %、活性度200.7 mmol/100g;脱色率93.65 %、活性度188.4 mmol/100g,所测指标都达到了HG/T2569-94行业标准,此技术的应用具有良好的社会效益、经济效益和环境效益。
Bentonite is an important non-metallic mineral,it is widely applied to many industrial fields. In our country,bentonite resource is quite abundant, but its master production is still in primary phase. Bentonite is activated and used for producing white carbon at the same time, which can not only produce goods with high added value but also meet the growing demand for the upper-end products, sequentially, utilize bentonite resource high-efficiently.
Bentonite in western Liaoning Province is chosen as raw material, this paper lucubrates the mechanism of preparation, draws up the better technological process, studies every technical parameter in the processes which include purification, activation and preparation of white carbon, obtains high-efficient activated clay and white carbon, at the same time, recycles acid pickle and confirms the optimal technical parameters.
After the bentonite is purified by means of sodium modification and dispersion, the experiment shows that the montmorillonite content is rising from 70.00% to 84.67%.
By means of single factor exploratory research and orthogonal test, the experiment confirms the optimal technological conditions in producing activated clay by wet method. Acid-clay ratio is 20%, activation time is 4h, activation temperature is 90℃, solid-liquid ratio is 4:1. According to the conditions, the production is tested. The performance testing results are as following. The decolouring ratio is 99.75%, the activity is 223.1mmol/100g, the free acid is 0.13%. These indicators precede the requests of the HG/T2569-94 industry standard.
The experiment studies preparation of white carbon by means of non-metallic minerals separation method. The optimal technological conditions which base on the single factor method are as following. Acid-clay ratio is 66%, acid dissolution time is 3h, acid dissolution temperature is 100℃, acid dissolution solid-liquid ratio is 4:1, alkali-clay ratio is 17%, alkali dissolution time is 3h, alkali dissolution temperature is 100℃, alkali dissolution solid-liquid ratio is 4:1, proportion of adding electrolyte is 1.5%, proportion of adding absolute ethyl alcohol is 10%, neutralization temperature is 80℃, pH=8, aging time is 30 min, aging temperature is 80℃, absolute ethyl alcohol is adopted to rinse the products in permutation. According to the conditions, the production is tested. The performance testing results are as following. The absorption value of Dibutyl Phthalate is 2.05ml/g, pH of the suspending liquid is 6.8, the heating loss is 4.0%. SiO2 content reaches 90.94%. These indicators are all in keeping with the requests of the HG/T3061-1999 industry standard.
Being based on the technical experimental research of recycling acid pickle from preparation of activated clay and white carbon, reducing acid dosage and saving water resource, the activated clay of different quality is obtained in the experiment. The production performance testing results are as following. The decolouring ratio is 97.37% and 93.65%, respectively, the activity is 200.7mmol/100g and 188.4mmol/100g. These indicators are all in keeping with the requests of the HG/T2569-94 industry standard. The application of technology will make favorable social, economic and environmental benefit.
引文
[1]姜桂兰,张培萍.膨润土加工与应用[M].北京:化学工业出版社,2005.13～78.
[2]栗文楼,李明路.膨润土的开发应用[M].北京:地质出版社,1998.4～20.
[3]郑秀华.膨润土应用技术[M].武汉:中国地质出版社,2001.1～30.
[4]郑水林.非金属矿加工与应用[M].北京:化学工业出版社,2003.68～69.
[5]韩秀山.膨润土的综合开发利用[J].橡胶参考资料,2004,34(4): 15～17.
[6]武占省.食用油脂脱色用高效活性白土的研制及其吸附性能研究[D].石河子大学,2006.6:7～9,21.
[7]韩秀山.非金属矿制备白炭黑的技术简介[J].化工设计通讯,2005,31(4):46～50.
[8]张秀娟,周产力.国内外白炭黑生产现状[J].无机盐工业,1995,(6):20～22.
[9]陈艳.云南砚山膨润土的提纯及改型改性研究[D].昆明理工大学,2007.4:8～10.
[10]单承湘,于少明,杨保俊.膨润土提纯方法的研究[J].合肥工业大学学报(自然科学版),1997,20(2):29～33.
[11]荣葵一,龙小庆,彭长琪.蒙脱石湿法提纯改型方法与原理[J].武汉工业大学,1996(3):19～22.
[12]童箔.钠基膨润土湿法提纯[J].非金属矿,1999(22):21～22.
[13]闫景辉,李景梅,王巍等.膨润土化学提纯研究[J].非金属矿,2002,25(3):8～10.
[14]吴东印,卫敏,杨建业.膨润土的湿法提纯研究[J].郑州综合利用研究所选矿室2000,23(3):23～24.
[15]莫文生.膨润土湿法提纯工艺研究[J].非金属矿,2002,25(6):33～34.
[16]王泽民,周凤歧,马小凡.膨润土的提纯及应用研究[J].非金属矿,1996,19(3):193～196.
[17]蒋月秀,黄大新,李仲民等.膨润土的纯化及脱水过程研究[J].广西科学,2003,10(2):110～112.
[18]耿爱芳,王巍,闫景辉.膨润土的提纯[J].长春光学精密机械学院学报,2001,24(4):44～45.
[19]吴东印,卫敏,杨康平,王建业.膨润土的提纯与开发应用[J].矿产保护与利用,2000,(3):14～16.
[20]甄卫军,庞桂林,李振江,蔡香丽.新疆夏子街钠基膨润土湿法提纯、有机化及应用研究[J].非金属矿,2005,28(6):43～46.
[21]牛炳昆.膨润土提纯研究[J].化工矿物与加工,1999,(8):6～8.
[22]文辉忠,赵临远.活性白土研究进展[J].化工纵横,2001,(10):5～7.
[23]张术根.活性白土湿法生产漂法方法研究[J].化工矿物与加工.2001,10(1):12～14.
[24]袁慰顺,孔炳炎.我国活性白土产业近况[J].浙江地质科技情报,2002,(1):7～9.
[25]傅铁铮.浅谈活性白土的生产工艺条件和参数对产品质量的影响[J].非金属矿,1993,(3):34～37.
[26]黎铉海,黄祖强,潘柳萍,等.膨润土酸活化工艺的实验研究[J].化工矿物与加工,2000,(10):7～9.
[27] Simon J.,Pollard T.,Christopher J.Sollars et al,Laboratory trials on bleaching palm oil with selected acid-activated Nigerian clays[J].Bioresource Technology,1993,45(1):53～58.
[28]杨志勤.活性白土的实验室研究[J].非金属矿,1995,(3):25～28.
[29]惠博然,李朝君.活性白土干法生产工艺及其改进[J].非金属矿, 1993, (3):30～33.
[30] Hymore,F.K.,Iyayi,A.F.,The performance of locally prepared adsorbents in the bleaching of palm oil[J].Nigerian J.Appl.Sci.,1988,6(2):17～30.
[31]王领贵,赵经贵,赵杰,等.利用拜泉膨润土制备活性白土的研究[J].黑龙江大学自然科学学报2003,20(2):117～119.
[32]黄彦林,周一民,英堂.河南信阳上天梯膨润土制备高效性白土实验研究[J].高校地质学报,2000,(2):292～293.
[33]张颖心,张天胜.承德低品位钙基膨润土制备高效活性白土的工艺研究[J].中国油脂,2002,27(5):46～49.
[34]陈强.信阳上天梯钙基膨润土胶溶法制备酸性膨润土新工艺研究[J].非金属矿,1999,22(2):10～11.
[35]谭钦德,陈淑荷.活性白土的制备[J].应用化学,1995,12(6):83～85.
[36]刘晓东,马小隆,吕宪俊.活性白土制备工艺条件优化研究[J].非金属矿,2004,27(3):30～33.
[37]张秀英,王萍,李国昌,等.利用膨润土生产活性白土的研究[J].矿产保护与利用,2004,(2):25～27.
[38]王德强.酸化对蒙脱石成分和结构影响的研究[J].矿物学报,1998,18(2):189～193.
[39]温淑瑶,马毅杰膨润土改性机理研究进展[J].污染防治技术,1999,12(3):178～180.
[40]王世杰.膨润土的酸化脱色机理研究[J].矿物学报,1993,13(4):325～330.
[41]郑舒文,林剑.白炭黑生产工艺的研究进展[J].辽宁化工,1999,28(6):340～342.
[42]韩秀山.膨润土的综合开发利用[J].化工文摘.2004,(2):50～51.
[43]熊剑,沉淀白炭黑的生成机理[J].江西化工,2004,(2):31～33.
[44]秦克刚,李淑珍.水玻璃模数的快速测定[J].理化检验-化学分册, 2000,36(10):472.
[45]张秀英.钙基膨润土制备白炭黑的研究[J].矿产保护与利用, 2005, (6): 21～24.
[46]侯太鹏,刘英魁.用膨润土制备白炭黑试验研究[J],非金属矿, 2000,23(1):26～28.
[47]宋恩玉.膨润土制粉状活性白土、颗粒白土、白炭黑、水玻璃探讨[J].非金属矿,1998,21(6):36.
[48]李贤年,胡振民.沉淀法白炭黑研制[J].浙江化工,1991,22(2):19～23.
[49]哈丽丹,卢晓泉.沉淀法制取白炭黑[J].牙膏工业,2000,(4):23～24.
[50]许莹,沈毅.沉淀法制备纳米白炭黑工艺参数的控制[J].化工矿物与加工,2004,(7):15.
[51]张颖心.膨润土的综合利用研究[D].天津科技大学,2002.12:48.
[52]赵柄国,郭锴,谢小平.白炭黑制备工艺对比表面积和吸油值的影响[J].无机盐工业,2006,38(5):23～26.
[53]张永华.生产活性白土的污染最小化技术[J].环境污染与防治,1999,21(5):34～36.
[2]栗文楼,李明路.膨润土的开发应用[M].北京:地质出版社,1998.4～20.
[3]郑秀华.膨润土应用技术[M].武汉:中国地质出版社,2001.1～30.
[4]郑水林.非金属矿加工与应用[M].北京:化学工业出版社,2003.68～69.
[5]韩秀山.膨润土的综合开发利用[J].橡胶参考资料,2004,34(4): 15～17.
[6]武占省.食用油脂脱色用高效活性白土的研制及其吸附性能研究[D].石河子大学,2006.6:7～9,21.
[7]韩秀山.非金属矿制备白炭黑的技术简介[J].化工设计通讯,2005,31(4):46～50.
[8]张秀娟,周产力.国内外白炭黑生产现状[J].无机盐工业,1995,(6):20～22.
[9]陈艳.云南砚山膨润土的提纯及改型改性研究[D].昆明理工大学,2007.4:8～10.
[10]单承湘,于少明,杨保俊.膨润土提纯方法的研究[J].合肥工业大学学报(自然科学版),1997,20(2):29～33.
[11]荣葵一,龙小庆,彭长琪.蒙脱石湿法提纯改型方法与原理[J].武汉工业大学,1996(3):19～22.
[12]童箔.钠基膨润土湿法提纯[J].非金属矿,1999(22):21～22.
[13]闫景辉,李景梅,王巍等.膨润土化学提纯研究[J].非金属矿,2002,25(3):8～10.
[14]吴东印,卫敏,杨建业.膨润土的湿法提纯研究[J].郑州综合利用研究所选矿室2000,23(3):23～24.
[15]莫文生.膨润土湿法提纯工艺研究[J].非金属矿,2002,25(6):33～34.
[16]王泽民,周凤歧,马小凡.膨润土的提纯及应用研究[J].非金属矿,1996,19(3):193～196.
[17]蒋月秀,黄大新,李仲民等.膨润土的纯化及脱水过程研究[J].广西科学,2003,10(2):110～112.
[18]耿爱芳,王巍,闫景辉.膨润土的提纯[J].长春光学精密机械学院学报,2001,24(4):44～45.
[19]吴东印,卫敏,杨康平,王建业.膨润土的提纯与开发应用[J].矿产保护与利用,2000,(3):14～16.
[20]甄卫军,庞桂林,李振江,蔡香丽.新疆夏子街钠基膨润土湿法提纯、有机化及应用研究[J].非金属矿,2005,28(6):43～46.
[21]牛炳昆.膨润土提纯研究[J].化工矿物与加工,1999,(8):6～8.
[22]文辉忠,赵临远.活性白土研究进展[J].化工纵横,2001,(10):5～7.
[23]张术根.活性白土湿法生产漂法方法研究[J].化工矿物与加工.2001,10(1):12～14.
[24]袁慰顺,孔炳炎.我国活性白土产业近况[J].浙江地质科技情报,2002,(1):7～9.
[25]傅铁铮.浅谈活性白土的生产工艺条件和参数对产品质量的影响[J].非金属矿,1993,(3):34～37.
[26]黎铉海,黄祖强,潘柳萍,等.膨润土酸活化工艺的实验研究[J].化工矿物与加工,2000,(10):7～9.
[27] Simon J.,Pollard T.,Christopher J.Sollars et al,Laboratory trials on bleaching palm oil with selected acid-activated Nigerian clays[J].Bioresource Technology,1993,45(1):53～58.
[28]杨志勤.活性白土的实验室研究[J].非金属矿,1995,(3):25～28.
[29]惠博然,李朝君.活性白土干法生产工艺及其改进[J].非金属矿, 1993, (3):30～33.
[30] Hymore,F.K.,Iyayi,A.F.,The performance of locally prepared adsorbents in the bleaching of palm oil[J].Nigerian J.Appl.Sci.,1988,6(2):17～30.
[31]王领贵,赵经贵,赵杰,等.利用拜泉膨润土制备活性白土的研究[J].黑龙江大学自然科学学报2003,20(2):117～119.
[32]黄彦林,周一民,英堂.河南信阳上天梯膨润土制备高效性白土实验研究[J].高校地质学报,2000,(2):292～293.
[33]张颖心,张天胜.承德低品位钙基膨润土制备高效活性白土的工艺研究[J].中国油脂,2002,27(5):46～49.
[34]陈强.信阳上天梯钙基膨润土胶溶法制备酸性膨润土新工艺研究[J].非金属矿,1999,22(2):10～11.
[35]谭钦德,陈淑荷.活性白土的制备[J].应用化学,1995,12(6):83～85.
[36]刘晓东,马小隆,吕宪俊.活性白土制备工艺条件优化研究[J].非金属矿,2004,27(3):30～33.
[37]张秀英,王萍,李国昌,等.利用膨润土生产活性白土的研究[J].矿产保护与利用,2004,(2):25～27.
[38]王德强.酸化对蒙脱石成分和结构影响的研究[J].矿物学报,1998,18(2):189～193.
[39]温淑瑶,马毅杰膨润土改性机理研究进展[J].污染防治技术,1999,12(3):178～180.
[40]王世杰.膨润土的酸化脱色机理研究[J].矿物学报,1993,13(4):325～330.
[41]郑舒文,林剑.白炭黑生产工艺的研究进展[J].辽宁化工,1999,28(6):340～342.
[42]韩秀山.膨润土的综合开发利用[J].化工文摘.2004,(2):50～51.
[43]熊剑,沉淀白炭黑的生成机理[J].江西化工,2004,(2):31～33.
[44]秦克刚,李淑珍.水玻璃模数的快速测定[J].理化检验-化学分册, 2000,36(10):472.
[45]张秀英.钙基膨润土制备白炭黑的研究[J].矿产保护与利用, 2005, (6): 21～24.
[46]侯太鹏,刘英魁.用膨润土制备白炭黑试验研究[J],非金属矿, 2000,23(1):26～28.
[47]宋恩玉.膨润土制粉状活性白土、颗粒白土、白炭黑、水玻璃探讨[J].非金属矿,1998,21(6):36.
[48]李贤年,胡振民.沉淀法白炭黑研制[J].浙江化工,1991,22(2):19～23.
[49]哈丽丹,卢晓泉.沉淀法制取白炭黑[J].牙膏工业,2000,(4):23～24.
[50]许莹,沈毅.沉淀法制备纳米白炭黑工艺参数的控制[J].化工矿物与加工,2004,(7):15.
[51]张颖心.膨润土的综合利用研究[D].天津科技大学,2002.12:48.
[52]赵柄国,郭锴,谢小平.白炭黑制备工艺对比表面积和吸油值的影响[J].无机盐工业,2006,38(5):23～26.
[53]张永华.生产活性白土的污染最小化技术[J].环境污染与防治,1999,21(5):34～36.