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添加造纸黑液/改性后黑液对水煤浆性能的实验研究

The Experimental Studies on Coal-water Slurry by Adding Paper-making/Modified Black Liquor

【作者】 李效其

【导师】 庞先勇;

【作者基本信息】 太原理工大学 , 物理化学, 2012, 硕士

【摘要】 造纸黑液是造纸工业制浆工程中产生的黑色废水经过浓缩之后的粘稠液体,由于其难以分离降解,气味恶臭难闻,排放到河流湖泊之中,给我们的环境造成了严重的污染危害。迫于环境的严峻形势,对造纸黑液废水的综合治理已经到了刻不容缓的地步。造纸黑液中的碱木素、腐殖酸、半纤维等均具有表面活性剂功能,其中的成分可以取代添加剂。煤泥是煤炭洗选加工的副产品,是由微细颗粒煤粉、粉化矸石、泥土和水组成的粘稠物。随着煤炭入选比例的增大和机械化程度的加大,煤泥的产量将会加大,这么多的煤泥排放堆积,而且容易被风化吹干,造成严重的黑色沙尘暴,也给土地和空气污染造成了严重的危害。因此,可以直接利用黑液取代水和添加剂与煤泥、原煤制备水煤浆,这样既有效处理了造纸黑液和煤泥的排放,减少了环境污染,同时还可以降低水煤浆的生产成本,实现黑液和煤泥的资源化再利用,也给人们带来了更多的经济效益和社会效益。本论文主要研究造纸黑液与煤泥、原煤制备水煤浆的成浆性,旨在研究黑液的表面活性剂功能,高效处理利用造纸黑液,节能减排,减少污染。首先,考察了使用稀释不同倍数的黑液与煤泥制成水煤浆的最高成浆浓度、流变性、静态稳定性,发热量等,以及改变pH对黑液煤浆的影响;其次,研究了黑液与原煤的成浆性;最后对黑液进行磺化改性,将改性后的黑液与煤泥、原煤制备水煤浆,比较改性前后煤浆的成浆性能。通过实验表明,黑液制备煤浆时能够表现出良好的表面活性剂功能,起到很好的活性作用;改性后黑液制备煤浆比改性前具有更好的表面活性功能。主要实验结果如下:1、黑液与煤泥制备煤浆的成浆性研究选取两种黑液1#黑液(山西鸿昌农贸有限责任公司)、2#黑液(山西合盛工贸有限公司),与煤泥制备水煤浆,研究其成浆性能。1#造纸黑液的添加量为7.2%时,煤粉粒度小于160目,制得煤浆最高浓度为67.44%,可使煤浆稳定性可维持20天保持良好,流动性A级;2#造纸黑液的添加量为12.5%时,制得煤浆最高浓度为67%,流动性为A,稳定性在一周以上通过改变黑液的pH,考察其对黑液煤浆的成浆性能,结果实验表明pH对两种黑液煤浆影响都较小。但从总体上看,1#黑液煤浆的成浆性能优于2#黑液煤浆的成浆性能。2、黑液与原煤制备煤浆的成浆性研究选用1#黑液与山西当地的四种原煤(临汾煤、离石煤、晋阳煤、太原煤)制备水煤浆,研究其成浆性能。通过实验的比较发现,造纸黑液对原煤的成浆性仍然能够表现很好的分散功能,且当黑液添加比例为12%时,其浆体的综合性能达到最佳状态,成浆浓度达到近64%,稳定性可达10天左右。pH对黑液与原煤制备的煤浆的影响也较小。3、黑液的磺化改性及改性后黑液煤浆的成浆性对选用的黑液(1#黑液)进行化学磺化改性,考察其磺化温度,磺化时间对煤浆的成浆性能的影响,通过实验研究,表明磺化的反应温度范围主要集中在75-100℃,反应时间为30-40min时,制取的水煤浆粘度较低,流动性较好;流动性在整体上也有少许改善,比磺化前有一定的提高;稳定方面,改性后制备的煤浆比磺化前稳定性提高3-5天。

【Abstract】 Black liquor is viscous and stiff waste component, which is generated by concentrating waste liquor which is produced in the process of pulp and paper industry. Black liquor has been bringing about a lot of serious harm on environmental pollution of china, because it is not easily resolved and degraded, and it can send out foul-smelling gas. It is urgent to solve paper-making black liquor in a comprehensive way, because experimental pollution has been seriously harmed. Lignin, humus acid and hemicellulose of the black liquor have the function of surface-active agent, so we can directly use the black liquor instead of water and additive to preparing coal slurry. Coal slime is viscous and stiff waste component whicn contain superfine powdered coal, gangue pulverization, dirt and water, which is the byproduct in the process of coal. The output of coal slime will be increased quickly along with the rapid developmet of coal industry and mechanization. So coal slime accumulate on the ground, and is easily weathered by wind and water, which could cause serious black sandstorm. And it does also a lot of harm to the ground and air seriously. So we can directly use the black liquor instead of water and additive to prepare coal slurry with coal slime and coal. Thus the discharge of paper-making black liquor and coal slime is improved effectively, which could phase down environmental pollution and cut down the cost of production for preparing coal slurry. Therefore we could achieve the goal of making use of black liquor and coal slime, and will benefit our economy as well as our community.This paper mainly study the slurry of preparing coal-water mixture by using blackliquor, coal slime and coal, and aims to study the function of surface active agent in black liquor, which all treat and utilize black liquor effectively. We should increase production and economize as much as possible, and reduce emission of carbon and environmental pollution. First, the black liquor which was made into different dilution times and coal slime were made into the coal black liqour slurry with excellent performance, and then maximum slurry concentration, rheology, static stability, calorific value, and changing the pH of black liquor on the properties of black liquor coal slurry were investigated. Then the properties of black liquor coal slurry by black liquor and coal. Finally, the black liquor was modified by sulfonation, then modified black liquor and coal slime and coal were made into coal slurry, and compare the coal slurry of unmodified and modified black liquor. It has been shown by c that the function of surface active agent in black liquor is very good on preparing coal-water mixture, which can act active function well. And modified black liquor of coal slurry is better than unmodified on surface active agent. The main conclutions are summarized as follows:1.Study of preparing slurry by using black liquor and coal slime Black liquor, which come from Shang Xi Hong Chang Agricultural Trade Limited Company (1#black liquor) and Shang Xi He Sheng Industry and Commerce Limited Company (2#black liquor), and coal slime was made into coal-water slurry, which is investigated. When the add content of1#black liquid is7.2%and the particle size of powdered coal is less than160item, the concentration of coal water mixture prepared is67.44%, liquidity will be A grade and the stability will retain almost20day in good condition. When the addition of2#black liquor is12.5%, the concentration of coal water mixture prepared is67%, liquidity will be A grade and stability will retain more than a week. The experiments showed that the effect of pH on2kinds black liquor slurry is small, by investigating black liquor slurry on changing pH. However, on the whole,1#black liquor slurry is better than2#black liquor slurry.2、Study of preparing slurry by using black liquor and coal1#black liquor, and Shan Xi local coal (Lin Fen, Li Shi, Jin Yang, Tai Yuan) was made into coal water slurry, whose slurry was investigated. Afer comparative experiments, it is indicated that the slurry of black liquor and coal is very good and dispersant of black liquor is proved well. When the addition of black liquor is12%, the concentration of coal water mixture prepared with coal is64%, whose slurry is best and tability will retain more than10days. The experiments also showed that the effect of pH on black liquor slurry with coal is not big.3、Modified black liquor by sulfonation and its black liquor slurry 1#black liquor was modified by sulfonation. The effect of sulfonated temperature and sulfonated time on coal slurry is investigated. It is shown by experimental investigation that when the ranfe of sulfonated temperature is75~100℃and reaction time is30~40min, the apparent viscosity of modified black liquor slurry is not relatively big, whose liquidity retain excellent. Compared to unmodified black liquor, modified black liquor slurry is relatively better on liquitity, and its stability has been increased3~5days.

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