CN1223168A - 热再生废酸的方法 - Google Patents
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Abstract
本发明涉及一种热再生废酸的方法,所说的废酸是洗涤在高温冶炼生产金属过程中所产生的含二氧化硫废气时形成的。根据该方法,该废酸被浓缩并给送到一级熔炼炉的气体空间内,从而该废酸热再生所需要的能量来自熔炼过程中所产生烟气的热容量。
Description
本发明涉及一种热再生废酸的方法，该废酸是洗涤在高温冶炼生产金属过程中所产生的含二氧化硫的废气时形成的。根据该方法，该废酸被浓缩并给送到一级熔炼炉的气体空间内，其中热再生该废酸所需要的能量来自熔炼过程中所产生烟气的热容量。
硫化矿和精矿熔炼过程中所产生的烟气主要含有二氧化硫、重金属、砷、卤素和其他化合物。由于废气内氧含量高时导致三氧化硫生成量增加并进一步造成洗涤气体中产生废酸，所以重要的是上述精矿尽可能完全燃烧并且在熔炼过程中所产生废气的氧含量尽可能低。现已发现，灰尘，尤其是含铜灰尘，能催化SO3的形成。SO3很可能是在废热锅炉内生成的，为了避免这种情况发生，必须使废气的氧含量低并且废空气的数量尽可能小。
所产生气体的洗涤可分为干式分离法和湿式分离法。干式分离法是通过一个熔炼炉实现的，其中由炉体气体空间排出的废气一般首先进入一个废热锅炉以回收气体的热含量。然后该气体进入一个电除尘器。气体中所含有的很大比例的重金属化合物，除了汞及其化合物之外，业已通过冷却分离。所产生的气体常常用来生产硫酸，这种情况下，在硫酸厂、洗涤器、洗涤塔和湿式电除尘器内进行气体的湿式分离。
气体湿式洗涤的目的是通过直接水冷进一步把所说的气体冷却到一个适宜的温度，并从气体中分离出固体和挥发性杂质，例如重金属、卤素、砷和硒。利用湿式洗涤，当SO3与水接触时也能把SO3从气体中分离出来成为废酸。所产生废酸的数量在给送到湿式洗涤内的二氧化硫数量的2～4％数量级，其H2SO4含量在10～30％的数量级。
由于废酸内含有废气中的重金属和砷，故据认为它是一种有害废物。如果该废酸不能给送到任何其他工艺，例如生产锌或者化肥，或者矿物浓缩，则一般用石灰中和该废酸并引入池塘，然而废酸中和以及石膏贮存的方法对于处理废酸问题来说很昂贵。即使该措施也进而受到新的更严格的环保要求的限制。
一种用来处理废酸的方法是在特别专门建造的单独炉体内进行废酸再生。这种方法不但特别适用于化学工程，而且适用于冶金工业。Sander,U．和Daradimos,G．发表在“化学工程进展”(1978),74,p57～67的文章“再生废酸”描述了这种方法。该文章认为把废酸再生为二氧化硫和水是一个巨大的吸热反应，该反应所需的能量为至少275KJ/mol，并且在1000℃以上的温度下进行最好。利用一些燃料把再生炉内的温度升高到一个充足的水平。该文章也认为最好在燃烧之前把废酸浓缩到H2SO4含量为70％。
根据本发明的方法，把要从硫化矿或精矿熔炼过程所产生废气中分离的废酸浓缩并给送回到一级熔炼炉内进入该熔炼炉的气体空间，在这里它根据下述反应再生为二氧化硫、水和氧气：
从该方程可看出，废酸被再生为二氧化硫、水和氧气。这时废酸再生中生成的二氧化硫和其余二氧化硫一起回收以便制备硫酸或者单质硫。
该方法的一个基本特征是废酸被给送到一级熔炼炉的气体空间内，这种情况下可利用废气的高热容量。当废酸被给送到一级熔炼炉的气体空间内时，废气的温度很高，通常在1000～1600℃的数量级(该废气从气体空间进一步被排放到废热锅炉内)。废酸返回到废气内能降低废气的温度，由于更低的温度能延长锅炉的使用寿命并降低锅炉应变，故从废热锅炉的角度来看温度降低是有利的。术语“一级熔炼炉”是指硫化矿或精矿被给送到的熔炼炉。例如在熔炼铜镍精矿时，一级熔炼炉是一种悬浮熔炼炉例如一种闪速熔炼炉、一种反射炉或一种转炉。在悬浮熔炼炉中，废酸有利地被给送到上升烟道内，通过上升烟道把热废气排放到废热锅炉中，然而废气也可给送到下一级熔炼炉的气体空间内，或者在偶尔情况下甚至给送到反应竖炉内。本发明基本的新颖特征通过所附权利要求书更显而易见。
一般认为如果废酸被给送到熔炼炉的气体空间本身(在这里精矿和氧气反应)内，则废酸再生所需的能量应单独供给到熔炼炉内，因为例如铜镍精矿的热容量在精矿与氧气的反应中被消耗掉，不足以用来再生废酸。在精矿热容量高的特殊情况下，可以把浓缩废酸给送到反应竖炉内，该情况下可显著提高所产生工业废气内的富氧程度。这种情况能降低从悬浮熔炼炉排放的气体数量，并提高由废热锅炉和气体洗涤设备的铜生产所决定的容量。
现已发现，由于在较低的温度下炉喉内积聚的灰尘数量可保持更少，故把废酸给送到一级炉-熔炼炉-的气体空间内可产生有利的结果，即连接熔炼炉与废热锅炉的风道或者说炉喉比以前更干净。实验证明废酸给送到气体空间内可以把进入锅炉的气体温度平均降低30～100℃。由于温度降低而造成的唯一缺点是废热锅炉内所产生的蒸汽量变小，即减小量对应于温度的降低，但通过该方法所达到的优点数倍于所说的缺点。现已发现，几乎所有的废酸都在气体空间温度下再生，故把废酸给送到废气内并没有提高锅炉内所产生的SO3数量。
下文参阅附图1进一步描述本发明，其中一级熔炼炉1是一种悬浮熔炼炉，紧随其后连接有废热锅炉2和一个电除尘器3。精矿、反应气体和所需的补充材料给送到反应竖炉4内，熔融颗粒由反应竖炉落到下一级熔炼炉5内。废气和烟尘通过上升烟道排放到废热锅炉。根据该图所示的布置，浓缩废酸沿箭头7的方向给送到一级熔炼炉的气体空间内，该情况下是给送到悬浮熔炼炉的上升烟道6顶部，在这里它根据如上所述的反应立即再生。
在现有技术的描述中业已指出，废酸在给送到熔炼炉气体空间之前首先进行浓缩是有利的。一般地，实施废酸浓缩的工艺为，首先通过间接真空蒸发法蒸发该废酸，使废酸浓度达到约50％，然后通过直接浸没蒸发法达到所要的废酸浓度70～80％。在浓缩过程中，废酸内所含的卤素和砷被蒸发到废气中并从废气被洗涤成为冷凝物，废酸内所含的重金属(Cu、Zn和Cd)硫酸盐以一水合物的形式析出。从沉淀池把废酸以金属硫酸盐晶体上面的溢液形式排出，其中要再生的废酸已除掉大部分杂质。浓缩废酸中的重金属总量在每升几克的数量级，卤素含量在每升几十毫克的数量级。
浓缩废酸中所含的重金属和卤素在循环中仍存留，但它们只稍微提高了从熔炼炉进入气体洗涤的废气和烟尘内的杂质水平。如果烟尘不给送到熔炼炉而是单独处理，就要有重金属和砷的单独排放途径。在其他情况下，金属硫酸盐一水合物晶体泥糊及其母液可作为重金属的排放途径并作为部分砷的排放途径，蒸发冷凝物可作为卤素和其余砷的排放途径。重金属(Cu、Zn和Cd等)硫酸盐晶体泥糊可以例如用作电解锌过程中的原材料。
下文参阅实施例进一步描述本发明，其中在铜闪速熔炼炉和镍闪速熔炼炉运行的生产规模试验中对废酸热再生进行研究。然而，该方法也适用于其它金属的熔炼过程，例如高温熔炼锌。
实施例1
把浓缩废酸(72％H2SO4)以整个熔炼炉的废酸生成速率即约20升/min给送到铜闪速熔炼炉的上升烟道内。通过耐酸喷嘴利用压缩空气分散把该废酸以细雾的形式喷进闪速熔炼炉的上升烟道。废酸压力为5巴，喷射空气压力为3巴。试验进行4小时。闪速熔炼炉的进料速度为80吨/小时，进入废热锅炉的废气流量为约20000Nm3/h。在锅炉后面相连的电除尘器之后测量气体的SO3含量。锅炉内的气体温度降低约25℃。SO3的再生率为90％。
实施例2
对镍闪速熔炼炉进行上述类似试验布置。试验进行约55小时。闪速熔炼炉的进料速度为25吨/小时，进入废热锅炉的废气流量为约12000Nm3/h。在锅炉后面相连的电除尘器之后测量气体的SO3含量。锅炉内的气体温度降低约60℃。
试验结果如表2所示。
| SO3含量g/Nm3(平均值) | 再生率(％) | |
| 试验前 | 10 | |
| 试验过程中 | 10 | 100 |
从上述实施例的试验结果可明显看到，在废酸的给送过程中SO3含量没有显著增大；如果废酸没有再生，则将导致在电除尘器之后测量的从铜闪速熔炼炉排出的废气中SO3含量增加约50g/Nm3，从镍闪速熔炼炉排出的废气中SO3含量增加约60g/Nm3。
从技术角度来讲，废酸喷入闪速熔炼炉上升烟道内的给送实施平稳，喷嘴内没有检测到磨损或者腐蚀的迹象。
Claims (11)
1一种热再生废酸的方法，所说的废酸是洗涤在高温冶炼生产金属过程中所产生的含二氧化硫的废气时形成的，使所说的废酸被浓缩并且在废酸再生之前除掉废酸中所含有的大部分重金属、卤素和砷，该方法的特征在于通过把所说的废酸给送到一级熔炼炉的气体空间内而实现该废酸的热再生。
2根据权利要求1的方法，其特征在于该一级熔炼炉是一种悬浮熔炼炉。
3根据权利要求1和2的方法，其特征在于该废酸给送到所说的悬浮熔炼炉的上升烟道内。
4根据权利要求1和2的方法，其特征在于该废酸给送到悬浮熔炼炉下部炉的气体空间内。
5根据权利要求1和2的方法，其特征在于该废酸给送到所说的悬浮熔炼炉的反应竖炉内。
6根据权利要求2的方法，其特征在于该一级熔炼炉是一种闪速熔炼炉。
7根据权利要求1的方法，其特征在于该一级熔炼炉是一种反射炉。
8根据权利要求1的方法，其特征在于该一级熔炼炉是一种转炉。
9根据权利要求1的方法，其特征在于该废酸被浓缩到H2SO4含量为70～80％。
10根据权利要求1的方法，其特征在于废酸再生所需的能量来自熔炼过程中所产生烟气的热容量。
11根据权利要求1的方法，其特征在于该一级熔炼炉内的温度为1000～1600℃。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI974456A FI103517B (fi) | 1997-12-09 | 1997-12-09 | Menetelmä pesuhapon termiseksi hajottamiseksi |
| FI974456 | 1997-12-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1223168A true CN1223168A (zh) | 1999-07-21 |
| CN1116916C CN1116916C (zh) | 2003-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98123084A Expired - Lifetime CN1116916C (zh) | 1997-12-09 | 1998-12-09 | 热再生废酸的方法 |
Country Status (19)
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| US (1) | US6180078B1 (zh) |
| JP (1) | JP4187330B2 (zh) |
| KR (1) | KR100432551B1 (zh) |
| CN (1) | CN1116916C (zh) |
| AR (1) | AR017806A1 (zh) |
| AU (1) | AU749609B2 (zh) |
| BG (1) | BG64002B1 (zh) |
| BR (1) | BR9805233A (zh) |
| CA (1) | CA2255812C (zh) |
| DE (1) | DE19857015B4 (zh) |
| ES (1) | ES2154998B1 (zh) |
| FI (1) | FI103517B (zh) |
| ID (1) | ID21440A (zh) |
| PE (1) | PE20000122A1 (zh) |
| PL (1) | PL330140A1 (zh) |
| RO (1) | RO120256B1 (zh) |
| RU (1) | RU2213046C2 (zh) |
| SE (1) | SE519099C2 (zh) |
| ZA (1) | ZA9810767B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107814361A (zh) * | 2017-09-30 | 2018-03-20 | 东营方圆有色金属有限公司 | 一种废硫酸的处理回收方法及装置 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FI109364B (fi) | 2000-12-20 | 2002-07-15 | Outokumpu Oy | Menetelmä pesuhapon väkevöimiseksi |
| JP4574884B2 (ja) * | 2001-03-27 | 2010-11-04 | 住友重機械工業株式会社 | 排ガス処理システムの硫酸回収方法及び硫酸回収装置 |
| FI110874B (fi) * | 2001-12-13 | 2003-04-15 | Outokumpu Oy | Menetelmä ja laitteisto metallurgisen sulatusuunin jätelämpökattilan kapasiteetin nostamiseksi |
| US7592290B2 (en) * | 2004-04-08 | 2009-09-22 | Sulzer Metco(Canada) Inc. | Supported catalyst for stream methane reforming and autothermal reforming reactions |
| FI20106156A (fi) * | 2010-11-04 | 2012-05-05 | Outotec Oyj | Menetelmä suspensiosulatusuunin lämpötaseen hallitsemiseksi ja suspensiosulatusuuni |
| FI124714B (en) * | 2013-10-25 | 2014-12-15 | Outotec Finland Oy | PROCEDURE AND ARRANGEMENTS FOR SUPPLYING GAS PROCESS FROM A SUSPENSION MIXTURE TO A REMOVAL HEATER |
| CN107010598B (zh) * | 2017-04-24 | 2023-08-11 | 鞍山创鑫环保科技股份有限公司 | 一种高浓酸洗废液再生工艺及*** |
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| CA544488A (en) * | 1957-08-06 | Badische Anilin- And Soda-Fabrik Aktiengesellschaft | Production of gases containing sulfur dioxide | |
| GB642128A (en) * | 1940-10-26 | 1950-08-30 | United Chemical And Metallurg | Improvements relating to methods of decomposition of waste sulphuric acid to sulphurdioxide |
| AT184921B (de) * | 1950-08-08 | 1956-03-10 | Basf Ag | Verfahren zur Aufarbeitung schwefelsäurehaltiger Massen auf schwefeldioxydreiche Gase |
| GB739483A (en) * | 1951-03-20 | 1955-11-02 | Wikdahl Lennart | Method of carrying out exothermic chemical reactions in the gaseous phase |
| FI49845C (fi) * | 1972-10-26 | 1975-10-10 | Outokumpu Oy | Sulfidimalmien tai -rikasteiden liekkisulatuksessa käytettävä menetelm ä ja laite. |
| DE2339859A1 (de) * | 1973-08-07 | 1975-02-27 | Metallgesellschaft Ag | Verfahren zur aufarbeitung waessriger abfallschwefelsaeure |
| DE2417005A1 (de) * | 1974-04-08 | 1975-10-09 | Metallgesellschaft Ag | Verfahren zur herstellung von kontaktschwefelsaeure |
| DE2432250A1 (de) * | 1974-07-05 | 1976-01-29 | Metallgesellschaft Ag | Verfahren zur aufarbeitung waessriger, organische verunreinigungen enthaltender abfallschwefelsaeure |
| US4155749A (en) * | 1978-05-31 | 1979-05-22 | Dravo Corporation | Process for converting non-ferrous metal sulfides |
| DE2839794C3 (de) * | 1978-09-13 | 1981-05-14 | Norddeutsche Affinerie, 2000 Hamburg | Verfahren zur Verarbeitung hüttenmännischer Zwischenprodukte, sulfidischer Erze und/oder Erzkonzentrate |
| SU865782A2 (ru) * | 1980-01-10 | 1981-09-23 | Предприятие П/Я В-8830 | Способ сульфатизирующего обжига сульфидных материалов |
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- 1998-11-26 AU AU94139/98A patent/AU749609B2/en not_active Ceased
- 1998-11-30 SE SE9804131A patent/SE519099C2/sv not_active IP Right Cessation
- 1998-12-02 PE PE1998001173A patent/PE20000122A1/es not_active Application Discontinuation
- 1998-12-04 BG BG102992A patent/BG64002B1/bg unknown
- 1998-12-04 AR ARP980106171A patent/AR017806A1/es unknown
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- 1998-12-08 KR KR10-1998-0053736A patent/KR100432551B1/ko not_active IP Right Cessation
- 1998-12-08 ID IDP981599A patent/ID21440A/id unknown
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- 1998-12-08 BR BR9805233-0A patent/BR9805233A/pt not_active IP Right Cessation
- 1998-12-09 DE DE19857015A patent/DE19857015B4/de not_active Expired - Fee Related
- 1998-12-09 JP JP34941098A patent/JP4187330B2/ja not_active Expired - Fee Related
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107814361A (zh) * | 2017-09-30 | 2018-03-20 | 东营方圆有色金属有限公司 | 一种废硫酸的处理回收方法及装置 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2154998A1 (es) | 2001-04-16 |
| AR017806A1 (es) | 2001-10-24 |
| BR9805233A (pt) | 2001-03-20 |
| FI103517B1 (fi) | 1999-07-15 |
| CN1116916C (zh) | 2003-08-06 |
| ID21440A (id) | 1999-06-10 |
| SE9804131D0 (sv) | 1998-11-30 |
| JPH11235515A (ja) | 1999-08-31 |
| AU9413998A (en) | 1999-07-01 |
| US6180078B1 (en) | 2001-01-30 |
| SE9804131L (sv) | 1999-06-10 |
| PL330140A1 (en) | 1999-06-21 |
| ZA9810767B (en) | 1999-05-31 |
| DE19857015B4 (de) | 2012-03-08 |
| AU749609B2 (en) | 2002-06-27 |
| PE20000122A1 (es) | 2000-03-03 |
| SE519099C2 (sv) | 2003-01-14 |
| CA2255812C (en) | 2009-02-10 |
| CA2255812A1 (en) | 1999-06-09 |
| KR100432551B1 (ko) | 2004-09-04 |
| BG64002B1 (bg) | 2003-09-30 |
| KR19990062893A (ko) | 1999-07-26 |
| DE19857015A1 (de) | 1999-06-10 |
| ES2154998B1 (es) | 2001-12-01 |
| BG102992A (en) | 1999-07-30 |
| RO120256B1 (ro) | 2005-11-30 |
| RU2213046C2 (ru) | 2003-09-27 |
| FI974456A0 (fi) | 1997-12-09 |
| JP4187330B2 (ja) | 2008-11-26 |
| FI103517B (fi) | 1999-07-15 |
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