CN1051717A - A kind of method with solid sulphide dregs cement from solid sulphide dregs in burning coal - Google Patents
A kind of method with solid sulphide dregs cement from solid sulphide dregs in burning coal Download PDFInfo
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- CN1051717A CN1051717A CN89108564A CN89108564A CN1051717A CN 1051717 A CN1051717 A CN 1051717A CN 89108564 A CN89108564 A CN 89108564A CN 89108564 A CN89108564 A CN 89108564A CN 1051717 A CN1051717 A CN 1051717A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
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本发明属于利用燃煤脱硫产生的废渣制作固硫渣水泥的技术领域。The invention belongs to the technical field of making sulfur-fixing slag cement by utilizing the waste slag produced in coal-fired desulfurization.
目前我国由于燃煤的SO2年排放量达974万吨/年，是我国许多地区酸雨频发的主要根源。根据全国环境保护科学技术长期规划，到2050年，我国能源结构中仍以煤为主，占70%，而含硫煤达40%以上。因此，治理燃煤中SO2的排放是环保的重要课题。At present, the annual emission of SO 2 due to coal burning in China reaches 9.74 million tons per year, which is the main source of frequent acid rain in many areas of our country. According to the long-term plan of national environmental protection science and technology, by 2050, my country's energy structure will still be dominated by coal, accounting for 70%, while sulfur-containing coal will reach more than 40%. Therefore, controlling the emission of SO 2 in coal combustion is an important topic of environmental protection.
煤碳脱硫的方法很多，主要有两大类：一类是燃烧前脱硫，如分采分运、水洗等;另一类是燃烧后脱硫，如排烟脱硫等，美日等国家多采用这种方法。由于上述这两种方法都需要增加专门设备，一次投资大。一般工业用层燃炉和煤粉炉的燃烧温度均在1100℃以上，在此温度下，煤中的硫酸盐和硫化物均将变为SO3逸入大气，污染环境。清华大学热能系改进和推广的循环床沸腾炉燃烧温度为800～950℃，还研制一种新型的脱硫剂。在煤中加入这种脱硫剂，则在燃烧过程中形成不分解的无水硫酸钙，可将煤中的80%以上的SO3固定在渣中，从而防止或大大减少SO3对大气的污染。但是由于加入脱硫剂，煤碳燃烧后排渣量增加25%以上，即使低灰分的优质煤，至少排渣量在30%左右。这些含有大量SO3的固硫渣如不及时处理，势必又造成环境的二次污染。目前国内尚无处理方法，国外只有联邦德国曾报导过利用含SO33～5%的沸腾炉灰制作砌筑水泥、道路路基胶结料、沥青材料的填充料等用途。There are many methods for desulfurization of coal, and there are two main categories: one is desulfurization before combustion, such as separate mining and transportation, washing, etc.; way. Because above-mentioned two kinds of methods all need to increase special equipment, one-time investment is big. Generally, the combustion temperature of industrial bed-burning furnaces and pulverized coal furnaces is above 1100°C. At this temperature, sulfate and sulfide in coal will become SO 3 and escape into the atmosphere, polluting the environment. The combustion temperature of the circulating bed fluidized furnace improved and promoted by the Department of Thermal Energy of Tsinghua University is 800-950 ° C, and a new type of desulfurization agent has also been developed. Adding this desulfurizer to coal will form non-decomposed anhydrous calcium sulfate in the combustion process, which can fix more than 80% of SO3 in coal in the slag, thereby preventing or greatly reducing the pollution of SO3 to the atmosphere . However, due to the addition of desulfurizers, the amount of slagging after coal combustion increases by more than 25%. Even for high-quality coal with low ash content, the amount of slagging is at least about 30%. If these sulfur-fixing slags containing a large amount of SO are not disposed of in time, they will inevitably cause secondary pollution to the environment. At present, there is no treatment method in China. Only the Federal Republic of Germany has reported the use of fluidized furnace ash containing SO 3 3-5% to make masonry cement, road subgrade cement, and asphalt material fillers.
本发明的目的，旨在治理燃煤脱硫对环境造成的二次污染，变废为宝。将含大量SO3的固硫渣制成固硫渣水泥，可望获得显著的环保效益和显著的经济效益。The object of the present invention is to control the secondary pollution caused by desulfurization of coal combustion to the environment, and turn waste into treasure. Making sulfur-fixed slag cement from sulfur-fixed slag containing a large amount of SO 3 is expected to obtain significant environmental benefits and significant economic benefits.
本发明的主要技术特点是将20～60%的固硫渣与80～40%的硅酸盐水泥熟料，根据需要（当固硫渣中SO3含量偏低时），也可加适量的二水石膏，共同磨细，即可制得标养28天强度是熟料强度的62～110%的合格固硫渣水泥。由于燃煤的温度合适（800～950℃），沸腾炉燃煤固硫渣具有比粉煤灰高的活性。The main technical feature of the present invention is to combine 20-60% of sulfur-fixing slag with 80-40% of Portland cement clinker, and an appropriate amount of Gypsum dihydrate, ground together, can produce qualified sulfur-fixed slag cement whose strength after standard curing for 28 days is 62-110% of clinker strength. Due to the appropriate temperature of coal combustion (800-950°C), fluidized furnace coal-fired sulfur-fixing slag has higher activity than fly ash.
本发明的优点是将含大量SO3的固硫渣，制成合格的固硫渣水泥，不仅可根治渣中SO3的二次污染，有显著的环保效益，而且变废为宝，又可望获得显著的经济效益。我国生产原煤按5亿吨计，其中有80%用作燃料，如果占燃料10%的含硫煤采用脱硫剂，则将会产生渣量（按占煤重的50%计）达2000万吨，将其中的一半制作水泥，可增加水泥1000万吨，并可节省二水石膏100万吨，相当于增加10个大型水泥厂的年产量，可获得10亿元以上的经济效益。The advantage of the present invention is that the sulfur-fixing slag containing a large amount of SO3 is made into qualified sulfur-fixing slag cement, which not only can radically cure the secondary pollution of SO3 in the slag, but also has significant environmental protection benefits, and can turn waste into treasure, and can Hope to obtain significant economic benefits. my country produces 500 million tons of raw coal, 80% of which are used as fuel. If desulfurizers are used for sulfur-containing coal accounting for 10% of fuel, the amount of slag (accounting for 50% of coal weight) will reach 20 million tons. , Making half of them into cement can increase cement by 10 million tons and save 1 million tons of dihydrate gypsum, which is equivalent to increasing the annual output of 10 large cement plants and obtaining economic benefits of more than 1 billion yuan.
下面将进一步描述本发明所提出的任务。The tasks proposed by the present invention will be further described below.
由于加入脱硫剂，沸腾炉渣中就含有大量的SO3，这种含大量SO3的固硫渣是以不溶性无水硫酸钙的形态存在。本发明的固硫渣水泥，当固硫渣含无水硫酸钙以SO3计为6～10%时，固硫渣与硅酸盐水泥熟料按3～4∶7～6比例混合，当固硫渣含SO3为3～6%时，在熟料中掺入1～3%的二水石膏。控制水泥中SO3总量符合国标GB 1344-85要求的≤3.5%，共同粉磨至通过80μ筛筛余≤8%，制得的固硫渣水泥28天强度达熟料强度的70～99%。当固硫渣中SO3含量为10～20%，将20%的固硫渣与80%的硅酸盐水泥熟料混磨至通过80μ筛筛余量＜8%，制得的固硫渣水泥28天抗压强度高于或不低于熟料强度。当固硫渣以其40～50%与60～50%的硅酸盐水泥熟料共同粉磨至通过80μ筛筛余量＜8%，制得的固硫渣水泥28天强度可达熟料强度的60%以上，水泥中的SO3＞3.5%但＜6%，不发生有害影响。Due to the addition of desulfurizer, the boiling slag contains a large amount of SO 3 , and this sulfur-fixing slag containing a large amount of SO 3 exists in the form of insoluble anhydrous calcium sulfate. For the sulfur-fixing slag cement of the present invention, when the sulfur-fixing slag contains anhydrous calcium sulfate as SO 6 ～10%, the sulfur-fixing slag and Portland cement clinker are mixed in a ratio of 3～4: 7～6, when When the sulfur-fixing slag contains 3-6% SO 3 , add 1-3% dihydrate gypsum to the clinker. Control the total amount of SO 3 in the cement to meet the requirements of the national standard GB 1344-85 ≤ 3.5%, and grind together until the sieve through the 80μ sieve ≤ 8%, the 28-day strength of the prepared sulfur-fixed slag cement reaches 70-99% of the clinker strength %. When the SO3 content in the sulfur-fixing slag is 10-20%, mix and grind 20% of the sulfur-fixing slag with 80% of Portland cement clinker until the sieve through the 80μ sieve is less than 8%, and the obtained sulfur-fixing slag The 28-day compressive strength of cement is higher than or not lower than the clinker strength. When 40-50% of the sulfur-fixing slag is ground together with 60-50% Portland cement clinker until the sieve through the 80μ sieve is less than 8%, the strength of the prepared sulfur-fixing slag cement can reach clinker in 28 days More than 60% of the strength, SO 3 in the cement > 3.5% but < 6%, no harmful effects.
实施例：Example:
1.固硫渣 SO3＝7.13%。1. Sulfur-fixing slag SO 3 =7.13%.
所用水泥熟料抗压强度为52.5MPa。The compressive strength of the cement clinker used is 52.5MPa.
固硫渣∶熟料＝30∶70，28天抗压强度为48.9MPa，强度比为0.93，水泥中SO3＝2.14%，初凝1小时58分，终凝4小时03分;固硫渣∶熟料＝40∶60，28抗压天强度为44.9MPa，强度比为0.86，水泥中SO3＝2.85%，初凝1小时58分，终凝4小时03分;固硫渣∶熟料＝50∶50，28天抗压强度为38.7MPa，强度比为0.72，水泥中SO3＝3.57%，初凝3小时58分，终凝6小时23分。以上安定性均合格。Sulfur-fixing slag: clinker = 30:70, 28-day compressive strength is 48.9MPa, strength ratio is 0.93, SO 3 in cement = 2.14%, initial setting is 1 hour and 58 minutes, final setting is 4 hours and 03 minutes; sulfur-fixing slag : clinker = 40: 60, 28 day compressive strength is 44.9MPa, strength ratio is 0.86, SO 3 in cement = 2.85%, initial setting is 1 hour and 58 minutes, final setting is 4 hours and 03 minutes; sulfur-fixing slag: clinker =50:50, 28-day compressive strength is 38.7MPa, strength ratio is 0.72, SO 3 in cement =3.57%, initial setting is 3 hours and 58 minutes, final setting is 6 hours and 23 minutes. The above stability is qualified.
2.固硫渣中SO3＝4.21，熟料强度为46.5MPa，用30%固硫渣，二水石膏2%，水泥中SO3总量2.16，水泥强度47.0MPa，强度比1.01;固硫渣40%，二水石膏1%，水泥中SO3总量2.16，水泥强度为44.7Mpa，强度比为0.96。以上凝结时间分别为初凝2小时38分和3小时05分，终凝4小时53分和4小时28分，安定性合格。2. SO 3 in the sulfur-fixing slag = 4.21, the clinker strength is 46.5MPa, with 30% sulfur-fixing slag, 2% dihydrate gypsum, the total amount of SO 3 in the cement is 2.16, the cement strength is 47.0MPa, and the strength ratio is 1.01; Slag 40%, dihydrate gypsum 1%, the total amount of SO 3 in cement is 2.16, the cement strength is 44.7Mpa, and the strength ratio is 0.96. The above setting times are respectively 2 hours and 38 minutes and 3 hours and 05 minutes for the initial setting, 4 hours and 53 minutes and 4 hours and 28 minutes for the final setting, and the stability is qualified.
3.固硫渣SO3＝4.21，熟料强度55.2Mpa，用30%渣，二水石膏2%，水泥中SO3总量为2.16，水泥强度49.9Mpa，强度比0.90，初凝2小时，终凝4.5小时;固硫渣40%，二水石膏2%，水泥中SO3总量为2.58，水泥强度46.9Mpa，强度比0.85，初凝2小时17分，终凝4小时57分。其它性能合格。3. Sulfur-fixing slag SO 3 =4.21, clinker strength 55.2Mpa, use 30% slag, 2% dihydrate gypsum, total amount of SO 3 in cement is 2.16, cement strength 49.9Mpa, strength ratio 0.90, initial setting 2 hours, The final setting is 4.5 hours; the sulfur-fixing slag is 40%, the dihydrate gypsum is 2%, the total amount of SO 3 in the cement is 2.58, the cement strength is 46.9Mpa, the strength ratio is 0.85, the initial setting is 2 hours and 17 minutes, and the final setting is 4 hours and 57 minutes. Other properties are qualified.
4.固硫渣SO3＝11.81%，熟料强度46.3Mpa，固硫渣与熟料之比为2∶8，水泥强度为51.4Mpa，强度比1.11，水泥中SO3总量为2.36，初凝53分钟，终凝2小时48分，安定性合格。4. Sulfur-fixing slag SO 3 =11.81%, clinker strength 46.3Mpa, ratio of sulfur-fixing slag to clinker 2:8, cement strength 51.4Mpa, strength ratio 1.11, total SO 3 in cement 2.36, initial The coagulation time was 53 minutes, the final coagulation time was 2 hours and 48 minutes, and the stability was qualified.
5.固硫渣SO3＝11.81%，熟料强度46.3Mpa，固硫渣与熟料之比为4∶6，水泥中SO3总量为4.72，水泥强度为43.0Mpa，强度比0.93，初凝4小时29分，终凝6小时28分，安定性合格。5. Sulfur-fixing slag SO 3 =11.81%, clinker strength 46.3Mpa, ratio of sulfur-fixing slag to clinker 4:6, total SO 3 in cement 4.72, cement strength 43.0Mpa, strength ratio 0.93, initial The coagulation time is 4 hours and 29 minutes, and the final coagulation is 6 hours and 28 minutes, and the stability is qualified.
6.固硫渣SO3＝11.81%，熟料强度47.1Mpa，水泥SO3总量5.9%，水泥强度36.4Mpa，强度比为0.77，初凝4小时19分，终凝7小时24分，安定性合格。6. Sulfur-fixing slag SO 3 =11.81%, clinker strength 47.1Mpa, total cement SO 3 5.9%, cement strength 36.4Mpa, strength ratio 0.77, initial setting 4 hours and 19 minutes, final setting 7 hours and 24 minutes, stable sex qualified.
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| CN89108564A CN1051717A (en) | 1989-11-16 | 1989-11-16 | A kind of method with solid sulphide dregs cement from solid sulphide dregs in burning coal |
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| CN89108564A CN1051717A (en) | 1989-11-16 | 1989-11-16 | A kind of method with solid sulphide dregs cement from solid sulphide dregs in burning coal |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997007071A1 (en) * | 1995-08-14 | 1997-02-27 | Bureau Of Administrative Service, The Chinese Academy Of Sciences | Process for producing heat and cement clinkers in one boiler, its products, the equipment used and its uses |
| CN1039638C (en) * | 1993-12-04 | 1998-09-02 | 郑伟明 | Portland cement containing sulphur-slag and its production |
| CN104402336A (en) * | 2014-10-30 | 2015-03-11 | 叶香菲 | Precast concrete slab prepared from waste concrete as aggregate |
| CN105198250A (en) * | 2015-10-20 | 2015-12-30 | 河南理工大学 | FBC (fluidized bed combustion) ash containing cement and preparation method thereof |
| CN106966619A (en) * | 2017-05-22 | 2017-07-21 | 山西大学 | A kind of fluidized bed combustion coal ash/slag cement and preparation method thereof |
| CN113831035A (en) * | 2021-09-01 | 2021-12-24 | 长江三峡技术经济发展有限公司 | Retarded cement prepared from solid sulfur ash and coal gangue and preparation method of retarded cement |
-
1989
- 1989-11-16 CN CN89108564A patent/CN1051717A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039638C (en) * | 1993-12-04 | 1998-09-02 | 郑伟明 | Portland cement containing sulphur-slag and its production |
| WO1997007071A1 (en) * | 1995-08-14 | 1997-02-27 | Bureau Of Administrative Service, The Chinese Academy Of Sciences | Process for producing heat and cement clinkers in one boiler, its products, the equipment used and its uses |
| AU713233B2 (en) * | 1995-08-14 | 1999-11-25 | Bureau Of Administrative Service, The Chinese Academy Of Sciences | Process for producing both steam power and cement clinker simultaneously in one apparatus its products, apparatus and use |
| US6468345B1 (en) | 1995-08-14 | 2002-10-22 | The Chinese Academy Of Sciences | Process for producing both steam power and cement clinker simultaneously in one apparatus its products, apparatus and use |
| CN104402336A (en) * | 2014-10-30 | 2015-03-11 | 叶香菲 | Precast concrete slab prepared from waste concrete as aggregate |
| CN105198250A (en) * | 2015-10-20 | 2015-12-30 | 河南理工大学 | FBC (fluidized bed combustion) ash containing cement and preparation method thereof |
| CN105198250B (en) * | 2015-10-20 | 2017-09-29 | 河南理工大学 | A kind of fluidized bed combustion coal ash/slag cement and preparation method thereof |
| CN106966619A (en) * | 2017-05-22 | 2017-07-21 | 山西大学 | A kind of fluidized bed combustion coal ash/slag cement and preparation method thereof |
| CN106966619B (en) * | 2017-05-22 | 2019-06-28 | 山西大学 | A kind of fluidized bed combustion coal ash/slag cement and preparation method thereof |
| CN113831035A (en) * | 2021-09-01 | 2021-12-24 | 长江三峡技术经济发展有限公司 | Retarded cement prepared from solid sulfur ash and coal gangue and preparation method of retarded cement |
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