CN1049294A - 用水泥窑尘浆液洗涤水泥窑废气的系统 - Google Patents
用水泥窑尘浆液洗涤水泥窑废气的系统 Download PDFInfo
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Abstract
本发明提供了一种工艺方法和设备，它能洗涤酸
性废气和去除水泥厂或类似工厂产生的废尘中的碱
金属和碱土金属盐，同时能将要废弃的物质转化成有
用的产物，其实质是使这两种废物流在水中化合，然
后在缶中分离所形成的溶液和沉淀，溶液用以冷却进
入的废气，并用作肥料，而沉淀适合作为窑原料。
Description
本发明涉及一种处理水泥厂产生的窑尘及废气的系统。此系统将窑尘转化成为有用的产品，同时去除废气中的污染物。
在烧制水泥或石灰的窑旁设置的窑尘收集装置可去除窑废气中的颗粒物质。随进窑原料的组成不同，这类颗粒物质可包括碳酸钙、氧化钙和其它金属的氧化物及碳酸盐。窑尘中经常含有的两种元素是钾和钠，这两种元素限制或妨碍窑尘作为原料的再使用，因为它们会影响最终产品的特性，所以窑尘要作废弃处理。由于窑尘收集装置不能有效地去除废气中的气态污染物，所以为防止污染物进入大气环境，就必须设置另外的洗涤装置。
多年来，固态或稀浆状或溶液状的碱金属或碱土金属已用于废气的洗涤(去除氧化硫和氧化氮)操作中(参看G.莫里森(Morrison)以前的讨论，这里作为参考文献引入)。例如梅尔门(Mehlmann)(水泥-石灰-石膏，版本B，1985)描述了在温度达1100℃下使用熟石灰石或粉末状石灰石，或采用熟石灰的喷雾干燥法；艾尔(Ayer)(1979，EPA-600/7-79-1676)描述了使用石灰洗涤供热工厂产生的废气。为达同样的目的，流化床炉的料中也可含有石灰石。通常，废气中存在氧化碳、氧化硫和氧化氮与水反应产生酸；如硫酸、亚硫酸、硝酸、碳酸。产生的酸类和酸量与废气中所含的氧化物、氧的供应量的反应条件有关。当这些酸与碱金属和碱土金属的氧化物、氢氧化物或碳酸盐反应时，形成相应的盐，例如硫酸与石灰石中的碳酸钙反应产生硫酸钙。
本发明的主要目的是要提供一种方法和设备，以解决水泥厂存在的窑尘处置问题，同时减少气态和颗粒状的排放物，并将废物转变成有用产品，达到经济实用的目的。
本发明提供了一种能去除窑尘中大部分钾、钠和硫的工艺方法，以使窑尘可作为原料再使用，同时本发明也提供了一种利用窑尘作为去除废气中氧化硫、氧化氮和氧化碳的反应剂的工艺方法。
更确切地说，这种工艺方法的功能为：使水泥窑尘或石灰窑尘与由废气中所含的硫、氮和碳的酸性氧化物产生的酸进行反应，以溶解窑尘中某些组分，并使其余的未溶解固体作为工艺原料再使用；洗出废气流中部分氧化硫、氧化氮和氧化碳，并使其与窑尘反应；产生一种碱金属和碱土金属盐副产品，它是由从废气中洗出的氧化硫、氧化氮和氧化碳与窑尘中所含物质所组成；利用废气流中的热以降低含碱金属和碱土金属盐的工艺物流中的水分含量。
本发明提供了一种能洗涤含有酸性氧化物的废气流，同时又能处理含有固体碱金属和碱土金属化合物的窑尘的工艺方法，此方法包括下列步骤：(a)使水和窑尘混合以形成碱性(pH＞7)溶液，(b)使废气流通过上述碱性溶液，由此溶液与气体反应形成碱金属和碱土金属盐溶液及含不溶性硅酸盐、铝酸盐和铁化合物及碱金属和碱土金属盐的沉淀物。
本发明的物点包括废气流通过碱性溶液之前的冷却和(或)脱水处理；利用碱金属和碱土金属盐溶液来达到冷却和(或)脱水目的；利用不溶性硅酸盐、铝酸盐和铁化合物与所述沉淀物，将它们加到水泥厂的原料中以生产水泥；利用废气中的热蒸发掉碱金属和碱土金属盐溶液中的水；利用碱性盐溶液中溶有的固体成分作肥料用；从水泥厂的窑中得到废气流的窑尘。
本发明的特点之一是提供了一种能将水泥窑产生的含有碱金属和碱土金属固体化合物的窑尘转化为适合作为窑原料用的产物的方法，它包括下列步骤：(a)使窑尘中的可溶性部分溶于水，以形成碱性溶液。(b)使窑中产生的废气通过上述溶液，由此气体和溶液反应形成碱金属和碱土金属盐溶液和适合作窑原料用的不溶性的硅酸盐、铝酸盐和铁化合物以及碱金属和碱土金属盐沉淀物。再一个特点是废气通过碱性溶液前先经冷却和脱水处理，为此利用了碱性溶液。同时还利用废气中的热蒸发掉碱性盐溶液中的水。
本发明的另一个特点是提供了一种工艺方法，它能将水泥窑产生的含有碱金属和碱土金属固体化合物的窑尘转化为适合作为窑原料用的产物，同时又能洗涤窑中产生的废气流，并产生适于用作肥料的碱金属和碱土金属盐，此方法包括下列步骤：(a)使窑尘溶于水，以形成碱性溶液。(b)使窑中产生的废气通过上述溶液，由此该溶液和气体反应以达到洗涤该气体的目的，同时形成碱金属和碱土金属盐溶液和适合作窑原料用的不溶性的硅酸盐、铝酸盐和铁化合物以及碱金属和碱土金属盐沉淀物。最后，蒸发碱金属和碱土金属盐溶液中的水，以产生适合作肥料用的浓溶液或沉淀物。
本发明也提供了一种系统，它能洗涤含有酸性氧化物的废气流，同时又能处理水泥窑产生的窑尘或含有碱金属和碱土金属盐的类似物。此系统包括下列装置：处理缶；使水和窑尘的混合物进入该处理缶的装置；为稀释该混合物向该处理缶补加水的装置；使废气通过该混合物，以与该混合物起反应，由此产生含其水溶性组分的溶液以与该溶液形成含酸性氧化物、碱金属和碱土金属盐以及其它不溶性化合物的稀浆的装置：沉降缶；使该稀浆从处理缶转移到沉降缶，以进行固液分离，使固体沉入缶底，而溶液保持在上部的装置；从沉降缶底排出固体的装置及从沉降缶上部排出液体的装置。
本发明提供的系统还包括热交换器、使废气在进入处理缶前先经过热交换器的装置和使来自沉降缶的液体通过热交换器的装置，由此废气流在热交换器中被冷却，而同时该液体被加热以去除其所含的水分。
本发明更进一步的目的、特点和优点，将通过下面的优选实例及附图的详细描述更明显地体现出来。
图1描绘了为实施本发明的一种系统。
图2给出了本发明工艺方法中，在与废气中氧化物起反应期间，从窑尘中去除氧化钾和氧化硫的效率图。
本发明包括输送固体碱金属和碱土金属化合物、窑尘、水及废气的方法和装置，还包括使这些物相先混合和反应，然后分离所形成的组分的方法和装置。
简单地说，酸性气体和碱性固体在处理缶中与水混合，并起反应形成浆液。沉降缶用于从该浆液里的水和溶解固体所形成的溶液中分离沉淀下来的和未溶解的固体。热交换器一结晶单元利用废气中的热能(包括潜热)来蒸发浆液中溶解的盐溶液中的水，同时使废气冷却以用于上述工艺过程。蒸发溶解的盐溶液中的水所需的热量可从热的废窑尘、窑尘与水的水化反应以及废气压缩时所得的能量中获得。
参看图1，由碱金属和碱土金属固体盐和水组成的浆液由连结窑尘和水的混合缶(未画出)的管线8流出，并经管线10泵入处理缶12，同时取自适当水源(未画出)的补加水经管线14加入到处理缶，以产生稀的浆液16。由水泥窑或沸腾器(未画出)来的废气经管线18进入热交换器22，经冷却后从热交换器排出。废气中冷凝出的水收集于热交换器22中，并经管线44进入处理缶12。然后，废气经管线23进入压缩机20，再经管线24送到位于处理缶底部的分布管26中。为防止固体沉入处理缶12的底部，可采用合适的方法来搅拌或再循环该浆液，例如使用循环泵27。
废气鼓泡通过由碱性固体和水组成的浆液16，并从该缶顶作为洗涤过的废气28排出。由处理过的固体、水和溶解物质组成的浆液16用泵32经管线30送往沉降缶34。在该沉降缶中，用泵38将沉下的固体36排出，而含盐的水泵入热交换器22，以冷却进入热交换器的废气。盐溶液37中的水经蒸发成蒸汽后经管线40排放到大气中，或该水先经蒸发，然后再冷凝成液体，以获取其潜热重复使用。盐溶液37中的盐在热交换器中经浓缩和(或)沉淀后经由管线42收集之。所收集的盐中，其阳离子组分主要是钙、钾、镁和钠，阴离子组分主要是硫酸根、碳酸根和硝酸根，盐的实际组成与所处理的窑尘的起始组成及废气的组成有关。
热交换器22是一种已知类型的两用的热交换器-结晶单元，此单元从废气中取得热量，并使用这种热量(包括废气中水分冷凝的潜热)来蒸发水。
整个系统均由以标准方式组合的熟知的部件构成，例如处理缶体积可为100万加仓，并装有气体分布及搅拌装置。沉降缶的体积可为10万加仓。这两缶均可用不锈钢或其它能耐高浓度碱性或酸性溶液的合适材料如橡胶制成。
本发明的基本工作原理是使在煅烧过程中产生的两废物流进行再化合及反应，以达互相中和，并产生有价值的有用副产品，同时利用了低品位热能。这两废物流分别是能在水中产生酸性溶液的气态氧化物和能在水中产生碱性溶液的来自水泥窑的废颗粒物质。
这两废物流在水中经部分溶解后，起反应达互相中和。水泥窑尘中含有过量的钾和(或)钠和硫酸盐时，本工艺方法使相当比例的未溶固体得到溶解，这些固体包括钙盐和镁盐，所以最后所得的固体适合作工艺原料使用。从热交换器-结晶单元排出的硫酸钾和其它的盐适合作肥料或作制备化学品的原料。同时，废气在穿过处理缶中的浆液时，可净化掉废气中所含的大量氧化硫和氧化氮，并形成硫酸盐和硝酸盐。
实例
下面的讨论涉及在中等规模的以湿法生产水泥的厂中使用本工艺方法的一个实例。
来自窑集尘室的废气用压缩机20以200000立方英尺/分的流量经管线18送入热交换器22，废气的组成是可变的，但大致含水29％，含二氧化碳25％，含氮36％，含氧10％，含氧化氮400-600ppm，含二氧化硫200ppm。在热交换器22中，废气被冷却，其中的水被冷凝，结果体积流量下降35％-40％。然后，废气由压缩机20经管线23被抽出，并经管线24送至分布管26，并与浆液16起反应，以除去大部分氧化硫和氧化氮。在实验室规模的试验中，可从废气中去除99％的SO2。
窑尘以8-12吨/时(干重)进入处理缶12，加水以产生含水达95％的稀浆。该浆液的含水量由废窑尘中的钾和钠的起始浓度决定，同时也与返回到窑进料系统的物料的所需浓度有关。与废气反应后，经处理过的浆液以约200加仓/分的流量泵送到沉降缶34。在该沉降缶中，固体发生沉淀，以形成含水约35％、含固体约65％的浆液，它位于由水和可溶性盐组成的溶液下面。浆液由泵38从沉降缶34中排出，并和约7.8吨/时(固体)的水泥厂的工艺原料相混合。水溶液以约200加仓/分的流量经出口管线37泵送到热交换器22，以冷却废气，同时蒸发溶液中的水以产生副产品盐。副产品盐经管线42排出，其产率约为8-12吨/天。副产品盐包括硫酸钾、碳酸钙和其他由钾、钙、镁、钠阳离子和碳酸根、硫酸根、硝酸根阴离子组成的盐。一部分硝酸盐将亚硫酸盐氧化成硫酸盐。
参看图2，图中给出了两次实验(KD-18和KD-20)的结果。结果表明，窑尘中碱金属和碱土金属盐从窑尘去除后，产生适合作窑原料用的窑尘产物，即钾盐的含量从约3％降到小于1.5％，硫酸盐的含量从约6％降到3％或更低。应指出，图2所描绘的例中，一开始就将窑尘的全部装料量放入处理缶中，然后再引入废气，这就解释了在A-M天期间内曲线的斜率变化。窑尘中钾、钠和硫酸盐浓度从实验开始到处理结束共减少了50％以上。样品A-M指的是连续的天数，在这些天内，从连续的处理过程中取样。
加入经处理过的窑尘对原料组成的影响示于下表，它以I型和II型水泥生产中标准的窑进料所含的每种氧化物的百分数来表示。在标有“窑尘以100吨/天加到进料中”和“窑尘以200吨/天加到进料中”的栏目中，明显地看到，窑尘以100吨/天和200吨/天的量加到常规进料中，仅稍微影响进料的组成。实验结果证明窑尘组成的主要改变是去除了SO3和K2O，未去除尽的K2O和SO3未使原料的组成灰发生明显的改变。
尽管这里公布并描述了一种实施本发明的优选方法和设备，但应该理解，这只是作为一种例证，而不是作为一种限制条件。本发明的应用范围仅由附后的权利要求中所给出的特征说明所限定。
表：处理过的窑尘对窑进料组成的影响型I 常规进料 窑尘以100吨/ 窑尘以200吨/
天加到进料中 天加到进料中SiO2 12.99 12.99 12.99Al2O3 3.57 3.59 3.61Fe2O3 1.45 1.53 1.61CaO 43.49 43.62 43.75MgO 2.83 2.81 2.78SO3* 0.18 0.23 0.28K2O 0.93 0.94 0.96损耗 35.83 35.45 35.07Si比 2.58 2.54 2.49Al/Fe 2.46 2.35 3.24型IISiO2 13.24 13.23 13.22Al2O3 3.33 3.35 3.38Fe2O3 1.77 2.03 2.09CaO 13.09 43.23 43.38MgO 2.66 2.64 2.62SO3* 0.19 0.24 0.29K2O 0.68 0.70 0.72损耗 35.20 34.85 34.49Si比 2.49 2.46 2.42Al/Fe 1.69 1.65 1.62
*硫酸盐以SO3表示
Claims (4)
1.一套工艺系统，该系统是用于利用废气的热使水泥窑废气与水泥窑废尘反应，从而除去了废料，回收了反应产物，该废气包括至少一种硫、氮、碳和囟素的酸性氧化物的污染物，该废尘包括碱金属和碱土金属盐，该系统包括下列装置：
热交换-结晶化设备、气-液接触处理缶、沉降缶和连接所述设备和缶的装置，该连接装置包括：
通过所述设备将废气导入气-液处理缶，并自处理后排出导入装置，
气体离升所述设备后移动和压缩气体的装置，
为了与气体反应，将水和水泥尘输入所述处理缶的输入装置，
将所述处理缶的反应液态和固体物移入所述沉降缶的装置，在沉降缶中，含有物分离成(a)固体和(b)含有可溶性盐的液体，该盐包括适用于做窑原料的硫酸钾和硫酸钠，
将上述(b)液体输入所述热交换-结晶设备中的输入装置，在热交换-结晶设备中，可使废气冷却同时加热液体达到蒸发点，从而使含有盐的液体结晶，用于以后的回收中。
2.按权利要求1的系统，其特征是还包括收集水的装置，该水是从所述热交换-结晶设备的废气冷凝而得，再加入到所述处理缶的水和水泥尘的混合物中。
3.按权利要求1的系统，其特征是还包括搅拌在所述处理缶中的水和水泥尘的混合物的装置。
4.按权利要求3的系统，其特征是其中所述搅拌装置包括：
泵和该泵与所述处理缶相联的管道装置，使所述混合物从处理缶内循环出来。
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| US7939336B2 (en) | 2008-09-30 | 2011-05-10 | Calera Corporation | Compositions and methods using substances containing carbon |
| TW201033121A (en) | 2008-10-31 | 2010-09-16 | Calera Corp | Non-cementitious compositions comprising CO2 sequestering additives |
| US9133581B2 (en) | 2008-10-31 | 2015-09-15 | Calera Corporation | Non-cementitious compositions comprising vaterite and methods thereof |
| BRPI0823394A2 (pt) | 2008-12-23 | 2015-06-16 | Calera Corp | Sistema e método eletroquímico de hidróxido de baixa energia |
| WO2010093716A1 (en) | 2009-02-10 | 2010-08-19 | Calera Corporation | Low-voltage alkaline production using hydrogen and electrocatlytic electrodes |
| CN101977842A (zh) | 2009-03-02 | 2011-02-16 | 卡勒拉公司 | 气流多污染物控制系统和方法 |
| WO2010104989A1 (en) | 2009-03-10 | 2010-09-16 | Calera Corporation | Systems and methods for processing co2 |
| US7993511B2 (en) | 2009-07-15 | 2011-08-09 | Calera Corporation | Electrochemical production of an alkaline solution using CO2 |
| DE102010019100A1 (de) * | 2010-04-30 | 2011-11-03 | Dko - Deutsche Kali Und Oxid Gmbh | Verfahren zum Gewinnen von Kalisalz aus einem Zementbypassprodukt in einer Industrieanlage, Verfahren zum Herstellen von Zement, Verfahren zum Gewinnen von Kaliumsulfat sowie Verfahren zum Gewinn von drei unterschiedlichen Salzen |
| CN107488021B (zh) * | 2017-09-30 | 2019-07-05 | 中晶蓝实业集团有限公司 | 基于臭氧氧化的胶凝材料的制造方法 |
| WO2021019754A1 (ja) * | 2019-08-01 | 2021-02-04 | 太平洋エンジニアリング株式会社 | 脱硫剤製造方法及び製造装置並びにセメントキルン排ガスの脱硫方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB111845A (en) * | 1916-12-02 | 1918-11-14 | William Griffith Henshaw | Improvements in Leaching Flue-dust. |
| DE1174681B (de) * | 1962-06-13 | 1964-07-23 | Polysius Gmbh | Verfahren zum Reduzieren des Alkalikreislaufs bei Zementbrennanlagen, insbesondere solchen mit Rostvorwaermern |
| US3507482A (en) * | 1968-11-08 | 1970-04-21 | Ludwik Kraszewski | Apparatus for reducing alkali content of cement clinker and simultaneously improving efficiency of electrostatic dust collector |
| US3687613A (en) * | 1970-10-27 | 1972-08-29 | Combustion Eng | Method and apparatus for preparing an additive for introduction to a gas scrubber |
| DE2166471C3 (de) * | 1971-08-23 | 1976-01-08 | Polysius Ag, 4723 Neubeckum | Verfahren zur Verringerung des Alkaligehalts von vorgewärmtem, einer Brennzone zuzuführendem Zementrohmehl |
| US3929968A (en) * | 1973-10-10 | 1975-12-30 | Du Pont | Dry collection of waste materials |
| JPS5848600B2 (ja) * | 1975-09-08 | 1983-10-29 | バブコツク日立株式会社 | セメントクリンカオモチイルコウオンダツリユウホウホウ |
| US4263264A (en) * | 1978-03-15 | 1981-04-21 | Nihon Cement Company Limited | Method of abating nitrogen oxides in combustion waste gases |
| GR75064B (zh) * | 1978-05-19 | 1984-07-13 | Niro Atomizer As | |
| US4228139A (en) * | 1979-03-06 | 1980-10-14 | Peabody Process System, Inc. | Flue gas scrubbing process using fly ash alkali |
| US4276272A (en) * | 1980-03-17 | 1981-06-30 | Kaiser Aluminum & Chemical Corporation | Cement waste product as scrubbing medium for sulfur oxides |
| US4584179A (en) * | 1984-05-18 | 1986-04-22 | Ramon Galli | Apparatus for treating cement kiln dust |
-
1986
- 1986-09-05 US US06/904,719 patent/US4716027A/en not_active Ceased
-
1987
- 1987-08-26 CH CH3268/87A patent/CH676555A5/de not_active IP Right Cessation
- 1987-09-02 KR KR1019870009696A patent/KR930012036B1/ko active IP Right Grant
- 1987-09-03 AT AT0222387A patent/AT396433B/de not_active IP Right Cessation
- 1987-09-03 TR TR87/0603A patent/TR24746A/xx unknown
- 1987-09-03 NZ NZ221664A patent/NZ221664A/xx unknown
- 1987-09-04 CN CN87105795A patent/CN1010083B/zh not_active Expired
- 1987-09-04 PL PL1987267595A patent/PL267595A1/xx unknown
- 1987-09-04 DK DK461487A patent/DK461487A/da not_active Application Discontinuation
- 1987-09-04 MX MX8116A patent/MX163666B/es unknown
- 1987-09-04 DE DE3729695A patent/DE3729695C2/de not_active Expired - Fee Related
- 1987-09-04 BE BE8700995A patent/BE1002111A4/fr not_active IP Right Cessation
- 1987-09-04 GB GB8720843A patent/GB2199314B/en not_active Expired - Fee Related
- 1987-09-04 ES ES8702564A patent/ES2005293A6/es not_active Expired
- 1987-09-04 BR BR8704632A patent/BR8704632A/pt not_active Application Discontinuation
- 1987-09-04 AU AU77961/87A patent/AU593681B2/en not_active Ceased
- 1987-09-04 ZA ZA876626A patent/ZA876626B/xx unknown
- 1987-09-04 FR FR878712327A patent/FR2603500B1/fr not_active Expired - Lifetime
- 1987-09-04 YU YU163587A patent/YU46227B/sh unknown
- 1987-09-04 CN CN90103222A patent/CN1049294A/zh active Pending
- 1987-09-04 GR GR871373A patent/GR871373B/el unknown
- 1987-09-04 JP JP62220570A patent/JPS63123843A/ja active Pending
- 1987-09-04 IT IT67762/87A patent/IT1223643B/it active
Also Published As
| Publication number | Publication date |
|---|---|
| BE1002111A4 (fr) | 1990-07-10 |
| DE3729695C2 (de) | 1994-09-15 |
| BR8704632A (pt) | 1988-04-26 |
| ES2005293A6 (es) | 1989-03-01 |
| AU7796187A (en) | 1988-03-17 |
| DE3729695A1 (de) | 1988-03-17 |
| DK461487D0 (da) | 1987-09-04 |
| GB8720843D0 (en) | 1987-10-14 |
| YU46227B (sh) | 1993-05-28 |
| AT396433B (de) | 1993-09-27 |
| MX163666B (es) | 1992-06-11 |
| JPS63123843A (ja) | 1988-05-27 |
| NZ221664A (en) | 1990-09-26 |
| AU593681B2 (en) | 1990-02-15 |
| PL267595A1 (en) | 1988-09-01 |
| ATA222387A (de) | 1993-01-15 |
| CH676555A5 (zh) | 1991-02-15 |
| DK461487A (da) | 1988-03-06 |
| GR871373B (en) | 1988-01-12 |
| CN1010083B (zh) | 1990-10-24 |
| KR930012036B1 (ko) | 1993-12-23 |
| FR2603500A1 (fr) | 1988-03-11 |
| TR24746A (tr) | 1992-03-09 |
| US4716027A (en) | 1987-12-29 |
| GB2199314A (en) | 1988-07-06 |
| CN87105795A (zh) | 1988-07-13 |
| IT1223643B (it) | 1990-09-29 |
| YU163587A (en) | 1989-10-31 |
| IT8767762A0 (it) | 1987-09-04 |
| ZA876626B (en) | 1988-05-25 |
| FR2603500B1 (fr) | 1991-02-15 |
| GB2199314B (en) | 1990-09-19 |
| KR880003660A (ko) | 1988-05-28 |
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