国内外低碳水泥的研究新进展

2017-08-21 10:27:04

近年来,随着全球对节能减排的呼声越来越高,传统水泥生产由于消耗大量资源和能源,以及产生大量的温室气体而面临巨大挑战。

  0 引言

  近年来,随着全球对节能减排的呼声越来越高,传统水泥生产由于消耗大量资源和能源,以及产生大量的温室气体而面临巨大挑战。资料显示,水泥工业能源消耗占全球一次能源消费的2%左右,或占全球工业能耗近5%;其CO2排放量占全球CO2排放总量的5%[1]。而对占全球产量近60%的我国水泥行业而言,水泥工业的节能减排显得尤为迫切。

  水泥生产过程中CO2排放源主要有:1)原料中碳酸盐分解;2)燃料的燃烧;3)各工艺设备的电力消耗。通用硅酸盐水泥生产中排放的CO2约有60%来自于碳酸盐分解,约有40%来自于燃料燃烧和电耗。通用硅酸盐水泥熟料中C3S矿物含量一般在60%左右,而由于C3S烧成温度较高,且配料中碳酸钙比例较大,因此生产时能耗较高,CO2及NOx的排放量也较大。因此,要实现水泥的低碳生产,可采用以下两种技术途径:一是降低能源消耗产生的CO2量,即在通用硅酸盐水泥体系及其矿物组成范围内,通过调控原材料的易烧性和易磨性,改进生产工艺及装备水平,降低水泥生产过程的能源消耗;二是降低碳酸盐分解产生的CO2量,即突破现有硅酸盐水泥熟料矿物体系及其矿物组成范围的限制,降低高钙矿物含量而提高低钙矿物含量或引入其他低钙矿物组分,研究开发新的低碳水泥体系。目前,水泥行业在第一种途径上已取得了良好进展,系列节能减排技术得到大规模普及利用,在现有技术条件下,依靠工艺技术及装备水平改造进一步实现节能减排难度已很大,而低碳水泥品种的研发成为当今水泥材料科学领域的热点。

  目前,国际上低碳水泥品种很多,有Porsol水泥、Alinit水泥、Celitement水泥、日本生态水泥、多组分高混合材掺量水泥、高贝利特水泥、Aether水泥、BCT水泥等,本文只对水泥生产工艺变化不大,可用目前新型干法水泥窑直接生产的高贝利特水泥、Aether水泥和BCT水泥进行了总结。

  1 高贝利特水泥

  水泥熟料中C3S矿物的生成焓为1810kJ/kg,而C2S矿物的生成焓仅为1350kJ/kg[2],所以增加熟料中C2S的含量并减少C3S的含量是降低熟料煅烧能耗的有效途径。因此,以C2S为主导矿物的低钙高贝利特水泥成为国际水泥工业最活跃的研究热点之一。

  以贝利特为主导矿物的低热硅酸盐水泥体系(C2S-C3S-C3A-C4AF,即高贝利特水泥,High Belite Cement)的研究源于20世纪30年代的美国。其于1932~1935年建造高99m的莫利斯(Morris)坝期间第一次研制了低热水泥,即限制水泥熟料中C3A和C3S的含量以降低水化热,这即是高贝利特水泥的原型。此外,德国、日本和瑞典等国家也都开展过相关的研究。至20世纪90年代,中国在高贝利特水泥的研究和实践应用方面卓有成效,在国内外首次实现以C2S为主导矿物的高性能低热硅酸盐水泥的工业化生产。

  高贝利特水泥和通用硅酸盐水泥在矿物组成上主要的差别在于C3S和C2S两种硅酸盐矿物含量的基本对调。高贝利特水泥以CaO含量相对较低的C2S为主(C2S含量一般为45%以上),从而使整个体系的CaO含量降低,其矿物组成为:C2S:40%~70%,C3S:10%~40%,C3A:2%~8%,C4AF:10%~25%[3]。其矿物种类与通用硅酸盐水泥相同,因此,其水化过程和水化产物也基本相同。

  高贝利特水泥使用的原料与传统硅酸盐水泥基本相同,需加入石膏、重晶石、黄铁矿、铜尾矿和铅锌尾矿等外加剂以稳定高活性C2S晶型[3]。高贝利特水泥在制备工艺上具有低资源能源消耗、低环境负荷等特点。如其烧成温度仅为1 350℃,比传统硅酸盐水泥低约100℃,烧成过程中CO2和SO2等的排放量降低10%,在水泥性能上具有低热和高后期强度等特性,很好地满足了大体积混凝土尤其是水工混凝土的技术要求,并在举世瞩目的三峡大坝等重点工程进行了规模应用。但与传统水泥相比,高贝利特水泥存在早期强度低的缺点。为此,水泥科研工作者做了大量努力,通过物理活化和化学活化等多种技术途径,改善了高贝利特体系的早期水化活性[4-8]。

  2 Aether水泥[9]

  Aether水泥是由拉法基公司研制发明的,并已申报发明专利。拉法基水泥公司于2010年成立了Aether项目组,历时3年(从2010年9月1日至2013年8月31日)进行了Aether低碳水泥的相关研究工作。Aether项目组完成了Aether水泥生产的2次工业试验,证实了依托现有的水泥窑炉工业化规模生产Aether水泥的可行性。

  Aether水泥可使用的原料包括:石灰石、铝土矿、石膏、铁质原料及泥灰岩。其引入硫铝酸钙(C4A3S)矿物,在较低的温度(1225~1300℃)下生产,相比波特兰水泥(1400~1500℃),可显著降低生产能耗,吨水泥可减少CO2排放量25%~30%。Aether水泥的矿物组成为:贝利特(C2S)40%~75%,硫铝酸钙(C4A3S)15%~35%,铁相(C2(A,F))5%~25%。Aether水泥相组成实例:C4A3S:35.5%,β-C2S:4.1%,α‘-C2S:44.0%,C12A7:0.7%,C2(A,F):12.4%,C2AS:0.9%,CaSO4:2.4%。

  Aether水泥水化过程:

  ① C4A3S 水化:

  C4A3S+2CS+38H→C3A·3CS·H32 +2AH3

  ② C2S 开始水化:C2S+AH3 +5H→C2ASH8

  ③ C2S水化、C2(A,F)开始水化:

      C2S+C2(A,F)+10H →C2(A,F)SH8+2CH

      C2S + C2(A,F)+5H→C3(A,F)SH4+CH

  ④ 中长期水化:

      2C2S+C2(A,F)SH8 +(x-4)H→C3(A,F)SH4 +C3S2Hx

  Aether水泥水化机理见图1。

图1 Aether水泥水化机理

  专业机构BRE(英国建筑科学研究院-英国领先的建筑专业技术中心)对Aether水泥的测试结果表明:由Aether水泥制备的混凝土拥有较高的早期抗压强度,其6h抗压强度可达20MPa左右,28d抗压强度达到标准水泥(CEMⅠ52.5R)强度水平;该混凝土的尺寸收缩小于OPC配制混凝土的50%,尺寸稳定性高于OPC水泥制作的混凝土。

  Aether水泥煅烧范围较窄(1225~1300℃),温度过低,矿物未完全反应,会产生C12A7和C2AS矿物,影响熟料质量;温度过高,C4A3S 矿物分解,SO2排放增加,易磨性变差。因此,需要严格控制煅烧温度,对工艺控制要求更高。

  由拉法基公司相关报道可以看出,Aether水泥与贝利特-硫铝酸盐水泥(贝利特-硫铝酸盐水泥矿物组成为C2S:40%~70%,C4A3S:15%~30%,C4AF:0~10%)非常相近,应为同一水泥熟料矿物体系。

  3 BCT水泥 [10-12]

  BCT水泥是Belite-Calciumsulfoaluminate-Ternesite水泥的简称,由德国海德堡公司发明,并已申请发明专利。采用直径0.3m、长7.6m的试验窑炉进行了半工业规模的试验,生产了数吨不同成分的BCT熟料。试验证明,BCT水泥熟料整个生产过程(包括排放)都与普通水泥熟料生产相似,生产的BCT水泥砂浆试验证明其性能良好。下一步将扩大至工业规模和优化制造技术。

  BCT水泥的核心技术是在熟料矿物体系中引入Ternesite即硫硅钙石矿物。硫硅钙石(C5S2S) 由2个C2S和1个CS 组成,一直被认为是惰性的,研究发现Ternesite是一种具有活性的熟料矿物,其水化反应介于铝酸盐和贝利特之间。与传统OPC水泥熟料煅烧过程中需要快速冷却以保留熟料的高反应活性不同的是,Ternesite形成温度在950~1 200℃之间,因此,BCT水泥熟料需要一个较慢的冷却过程或者说在烧成带后一个相对较长的停留时间。

  BCT水泥生产需要的原材料与普通硅酸盐水泥相近,石灰石、泥灰岩、粉煤灰和工业副产石膏等工业废渣都是其原料来源。BCT水泥熟料中引入硫铝酸钙(C4A3S)和硫硅钙石(C5S2S),在较低的温度(1250~1300℃)下生产,CO2排放比传统OPC水泥熟料降低30%,预计将节约燃料和电力消耗10%~15%。BCT水泥熟料的矿物组成为:C5S2S :5%~75%,C2S:1%~80%,C4(AxF1-x)S :5%~70%,二次相(secondary phases):0~30%。(专利保护范围)最佳矿物组成为:C5S2S :20%~0%,C2S:20%~50%,C4(AxF1-x)S:20%~45%,二次相:10%~20%。

  x取值范围为0.1~1,优选在0.8~0.95。

  BCT水泥水化过程:

  ①当BCT水泥与水接触时,C4A3S快速与硫酸盐形成钙矾石。因此,第一个24h占主导地位的是C4A3S 与硬石膏反应形成钙矾石。

  C4A3S+CS+H→C3A·3CS·H32+AH3

  ② 硬石膏一旦耗尽,剩余的铝酸盐相和铁相继续溶解并与Ternesite反应通过消化Al(OH)3形成更多的钙矾石和AFm。

  C4A3S+C4AF+C5S2S+AH3→C2ASH+C3A·3CS·H32+C3A·CSH12

  ③ 最后贝利特反应形成C-S-H凝胶:

  C2S+H→C-S-H+CH

  最终的水化产物为C(A)SH凝胶、AFt、AFm、潜在的水榴石和羟钙石。

  该品种水泥综合了硫铝酸钙的早期强度和贝利特水泥的耐久性,并通过Ternesite填补了迅速反应的铝酸盐和提供后期强度的贝利特的反应空白区间。基于Ternesite的水化特点,其除了可作为BCT水泥的一种矿物组分外,还可以作为一种添加剂用于硫铝酸盐基和硅酸盐基水泥胶凝材料系统中以改善性能。

  4 结论

  上述三类以低钙矿物C2S和C4A3S为主导矿物的熟料体系中,除硅酸盐体系的高贝利特水泥外,其他各类体系的水泥均引入一种以上的低能耗、低钙、高早强矿物,如C4A3S、C5S2S等。高贝利特含量和引入低钙早强矿物成为国际低碳水泥研究的趋势。

  然而,从Aether水泥和BCT水泥体系的研究来看,C4A3S和C5S2S在1300℃会发生分解,因此,引入此矿物的水泥熟料体系烧成范围窄,对工艺过程控制水平提出了更高的要求;另外,在体系中过多地引入上述低钙早强矿物,也不利于实现水泥体系高性能化。在水泥性能方面,尽管这些体系的水泥具有较高的早期强度特征,但在施工性能及水泥耐久性方面都相应带来了不利影响,例如含C4A3S 体系的水泥,凝结过程则较难控制,因此在绝大部分情况下,也仅仅作为特种工程材料使用,限制其大范围推广应用。

  笔者认为,如果能将目前中国建筑材料科学研究总院研究推广的能源管控系统应用于含低钙矿物的Aether水泥和BCT水泥的生产控制中,将可显著提高工艺控制水平,更好地实现低碳水泥的工业化生产。而对于水泥性能方面的影响,有研究表明硫铝酸钡钙C(4-x)BxA3S 的稳定性优于C4A3S,因此可通过掺杂等形式使C4A3S和C5S2S等低钙矿物更加稳定化以实现水泥性能优化。

  参考文献:

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[4] SUI Tongbo, GUO Suihua, LIU Kezhong, et al. Research on high belite cement[C]//4th Beijing International Symposium on Cement and Concrete. Beijing: China Academic Publishers, 1998:145-148.

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[9] http://www.aether-cement.eu/.

[10] Wolfgang Dienemann, Dirk Schmitt, Frank Bullerjahn, et al. Belite-Calciumsulfoaluminate-Ternesite(BCT) - a new low carbon clinker technology[C]//VDZ Congress 2013(7th International VDZ Congress "Process Technology of Cement manufacturing").

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[12] Heidelberg cement Ag. Calcium sulfoaluminate cement with ternesite,WO 2013023728 A2.

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As at the end of the reporting period, the total annual production capacity of cement clinker of the Company was approximately 18 million tons, the total annual production capacity of cement was approximately 20 million tons, the annual waste heat power generation capacity was approximately 86 MW, the total annual production capacity of commercial concrete was approximately 600,000 cubic meters, and the total annual production capacity of aggregate was approximately 18 million tons.

2025-04-25 10:04:31

On April 25, 2025, Shangfeng Cement (stock code: 000672), an A-share listed company, released its 2024 annual report and 2025 first quarterly report. In 2024, Shangfeng continued to demonstrate its excellent operational capability, and still achieved a revenue of 5.448 billion yuan and a net profit of 474 million yuan after deducting non-attributable profits despite cyclical fluctuations in the cement industry.

2025-04-25 10:01:50

On the evening of April 24, Shangfeng Cement released its annual report and quarterly report, while highlighting a new five-year development plan and a dividend scheme with a dividend rate of up to 7.5%. In the case that the scale of production capacity has not entered the top ten of the industry, the company's annual net return to the parent company ranks third among the listed companies in the industry, the comprehensive gross profit rate ranks first among the listed companies in the industry, and the net return to the parent company in a single quarter increases by 447.6%. While maintaining the high efficiency of the main business, the company's equity investment performance is outstanding, and a number of invested semiconductor science and technology enterprises have started to declare for listing one after another, and the newly released five-year planning report also clearly shows that the accumulation of its series of new economic equity investment will help the company to improve its quality and transformation.

2025-04-25 10:00:21

Iraq's prime minister launched a package of industrial projects on Thursday, mostly in the cement sector. Masna Province has launched six projects with a total investment of more than US $1.17 billion, including five cement projects and one chemical project. These projects help to achieve self-sufficiency in cement, reduce construction costs and create employment opportunities. Iraq's industrial development is facing many challenges. Since 2003, its industrial base has been destroyed and its economy is dependent on oil exports. However, the launch of this project is an important step to promote the strategy of economic diversification and lay the foundation for long-term development.

2025-04-25 09:53:11

The content shows that the replacement capacity of Xin'an Zhonglian Wanji Cement 4500t/d clinker production line is 1300t/d, and the capacity after replacement is 5800t/d. The transferred capacity comes from the 2500t/d clinker production line of the same company, which is used for the current capacity of 1300t/d, and the replacement ratio is 1:1.

2025-04-25 09:28:11

China Cement Network Market Data Center News, April 24, the Henan region again notified an increase in cement prices of about 20 yuan/ton. However, the current sales volume is 4-5% of the normal, and the demand is still low. After the opening of the kiln in early April, the cement clinker inventory of the enterprise has increased, and the implementation of the price increase remains to be observed.

2025-04-25 09:25:57

The market price of C30 concrete in Inner Mongolia ranges from 265 yuan/m3 to 315 yuan/m3, showing certain regional differences. Haraqin Banner in Chifeng City of Inner Mongolia has the highest price of 315 yuan per square meter, while Qingshuihe County and Tuoketuo County in Hohhot City of Inner Mongolia have the lowest price of 265 yuan per square meter.

2025-04-24 16:01:31

Since April 24, Henan has again notified the increase of cement price by about 20 yuan/ton, and the implementation remains to be observed..

2025-04-24 15:49:18

Since April 23, cement enterprises in Guiyang, Anshun, Tongren and other areas have been notified to raise the price of cement by about 30-60 yuan/ton, and the implementation remains to be observed..

2025-04-24 15:39:11

June this year is the 24th National "Safety Production Month", with the theme of "Everyone talks about safety, everyone will respond to emergencies-to find potential safety hazards around us", and June 16 is the National "Safety Publicity and Consultation Day".

2025-04-24 15:18:38

Implementing the negative list system of market access is an important decision-making arrangement made by the Party Central Committee and the State Council, and an important institutional arrangement for building a high-level socialist market economic system.

2025-04-24 14:39:18

The building materials industry carries out the docking activities of green building materials supply and demand and the cooperation and docking activities of inorganic non-metallic new materials industry chain. Implement the national cement production capacity management policy, guide the cement industry to carry out differentiated peak staggering production, and promote the recovery of cement prices.

2025-04-24 11:03:11

In accordance with the relevant provisions of the Company Law of the People's Republic of China and the Articles of Association of CCCC Shanghai Dredging Co., Ltd., the first meeting of the seventh session of the board of directors of CCCC Shanghai Dredging Co., Ltd. unanimously passed the following resolution: agreed to dismiss Wang Minqiu as the general manager of CCCC Shanghai Dredging Co., Ltd.; agreed to appoint Ding Jian as the general manager of CCCC Shanghai Dredging Co., Ltd.

2025-04-24 10:56:32

The content shows that there are 36 cement enterprises in the list in 2024 and 2025.

2025-04-24 10:52:51

The existing new dry process cement clinker production line with a daily output of 2500 tons (Φ4.0 * 60m) will be merged into a new dry process cement clinker production line with a daily output of 4000 tons (Φ4.8 * 72m) (i.e. 2 # clinker line). The total capacity will remain unchanged after the merger.

2025-04-24 10:42:22

On the evening of April 23, Tianshan Stock Company issued a quarterly performance announcement, saying that the revenue in the first quarter of 2025 was about 14.947 billion yuan, a decrease of 8.64% compared with the same period last year. The net profit loss attributable to shareholders of listed companies was about 1.494 billion yuan. The basic earnings per share loss was 0.2101 yuan. The revenue in the same period last year was about 16.359 billion yuan; The net profit loss attributable to shareholders of the listed company was approximately RMB1.923 billion, and the basic earnings per share loss was RMB0.222.

2025-04-24 10:03:28

Beginning in 2024, according to the requirements of the relevant policy documents of the Ministry of Industry and Information Technology, the cement industry began to fill the overcapacity. According to the statistics of China Cement Network, as of April 23, 57 production lines in the national cement industry had completed their production capacity, with a total of 19.45 million tons of cement clinker production capacity, and at least 41 production lines had been withdrawn, with a total capacity of 31.65 million tons.

2025-04-24 10:01:53

In 2024, the output of cement industry in the United States declined by 4.44%, and the dependence on imports increased. The decline in production was affected by factors such as factory closures, and domestic consumption was generally stable but seasonal differentiation. It imports 24 million tons of cement from many countries. Rising cement prices in the United States, the Trump administration's tariff policy brings uncertainty, if the tariff on Canada and Mexico has a significant impact, although American cement companies may benefit, there are also risks such as supply shortage, and some enterprises are more "Americanized".

2025-04-24 10:00:03

Xizang Langxian Gaozheng Building Materials Co., Ltd. intends to build a 4000t/d cement clinker production line project (hereinafter referred to as "Langxian Project") in Nyingchi City Langxian County by means of capacity replacement within the autonomous region.

2025-04-24 09:43:00

How to meet the "new deal of carbon emissions"? Li Kunming suggested that enterprises should work in a "three-pronged approach" from the production side, management side and market side to improve energy efficiency, increase investment in technology, establish professional teams, strengthen accounting and monitoring, and use financial instruments to actively participate in the market.

2025-04-24 09:24:04

Since April 23, the main cement enterprises in Liaozhong area have again notified the increase of cement price by 10 yuan/ton.

2025-04-23 17:24:32

The market price range of C30 concrete in Tianjin is between 280 yuan/m3 and 290 yuan/m3, showing some regional differences. Jinnan District has the highest price of 290 yuan per square meter, while Jizhou District and Xiqing District have the lowest price of 280 yuan per square meter.

2025-04-23 17:14:42

Recently, affected by the market situation, coupled with the poor implementation of the policy of staggering peak and stopping kilns, cement prices in Wuhan have fallen again, with a cumulative decline of about 30 yuan/ton..

2025-04-23 16:45:10

Relevant technicians of Suzhou Shijing Science and Technology Co., Ltd. pointed out that SCR is a very mature denitrification technology, which has been widely used in power and other industries. However, the cement industry still needs to focus on the catalyst, soot blower and reaction tower flow field to further optimize the three aspects.

2025-04-23 15:08:00

For a long time, cement has been the main loading and unloading cargo in Changgang Port. Faced with the continuous decline of domestic cement market demand in recent years, Changgang actively responded to the situation, actively sought change, timely adjusted the market development strategy, and took the development of foreign trade cement market as an important breakthrough in transformation and upgrading through comprehensive consideration of the domestic and foreign cement market.

2025-04-23 13:40:23

On April 21, information from the Beijing Property Exchange showed that 51% of the shares of Xin'an Zhonglian Wanji Cement Co., Ltd. held by China United Cement Group Co., Ltd. were listed for transfer at a base price of about 200 million yuan.

2025-04-23 11:50:52

Price governance is an important part of macroeconomic governance. In order to further deepen the price reform and improve the price governance mechanism, with the consent of the Party Central Committee and the State Council, the following opinions are put forward.

2025-04-23 10:34:13

The two sides will deepen cooperation around green building materials, new energy materials, circular economy and other fields, jointly create a new benchmark for the coordinated development of the industrial chain, and inject new momentum into the construction of "three places and one district" in Anhui.

2025-04-23 10:18:33

According to the announcement, the production capacity of Luoyang Huanghe Tongli Cement Co., Ltd. is 5000t/d after the cement clinker production line with a daily output of 4500 tons is completed. The replacement capacity for this project is 1000t/d of the 2000t/d clinker production line of Henan Tongli Cement Co., Ltd., and the replacement ratio is 2:1.

2025-04-23 10:13:11