CN101283064B - 包覆炉渣 - Google Patents
包覆炉渣 Download PDFInfo
- Publication number
- CN101283064B CN101283064B CN2006800375896A CN200680037589A CN101283064B CN 101283064 B CN101283064 B CN 101283064B CN 2006800375896 A CN2006800375896 A CN 2006800375896A CN 200680037589 A CN200680037589 A CN 200680037589A CN 101283064 B CN101283064 B CN 101283064B
- Authority
- CN
- China
- Prior art keywords
- slag
- urethane
- coated
- compound
- hydrophobicity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002893 slag Substances 0.000 title claims abstract description 81
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- 229920002635 polyurethane Polymers 0.000 claims abstract description 10
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/16—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/488—Other macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C04B41/4884—Polyurethanes; Polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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Abstract
本发明涉及包覆的炉渣,特征在于其被疏水性聚氨酯层包覆。
Description
本发明涉及疏水性聚氨酯包覆的炉渣。
在许多工艺中可得到炉渣,特别是在冶金中。取决于生产工艺,可将炉渣分为高炉渣、熔炼渣和钢厂炉渣。取决于工艺,这些炉渣可在实际生产过程中作为副产物由金属矿石、焦炭、石灰石和白云石产生。高炉渣一般用作水泥原料以及用于道路建设,个别情况下也用作肥料。得到的稍少量的钢炉渣主要用在建筑材料领域,而较小程度上用作肥料。一小部分,一般约10%,在垃圾掩埋中处理掉。
一部分钢炉渣除用于道路建设外也用在水利工程中。关于水利工程石材的基本要求在“Technische Lieferbedingungem für Wasserbausteine”中有所规定,包括关于岩石密度、尺寸和重量分类、石材形状、抗压强度、抗冻性及体积稳定性的要求。目前在水利工程中所用的炉渣经常替代以前用网格结构制造的结构体。一般,炉渣石材不再以复杂的方式放置而是任意倾倒。
使用炉渣的缺点首先是机械稳定性不足。因而,人们已发现在水利工程中应用时,有例如10~20%的炉渣崩解为非常细的颗粒尺寸。此粉碎过程随时间推移导致几乎不透水的胶结,因而构成顶层潜在的断裂点。
此外,需要避免有毒物质从炉渣释放到环境中或在水利工程情况下释放到水中。结果,担心导致对生物群落以及同时对水体的自清洁能力的不利影响。
现有技术公开了与塑料结合的炉渣用于土木工程和水利工程。
因而,DE 1 946 469描述了用于倾斜表面,特别是水利工程中的倾斜表面的密封层,此密封层由石材、炉渣和粘合剂组成。使用的粘合剂特别是沥青和热塑性塑料。通过向粘合剂中加入塑料防止了密封层流走。
美国专利申请-请***编号-和KR 2002008805描述了在道路建设中使用炉渣和聚合物树脂作为材料。据说这是为了增加材料的强度。
JP 2001163649描述了包含无机材料,例如含硫熔体包覆的工业废料的混合料。这给出<44mm的建筑材料,其可用于道路建设,也可用在海岸区域。通过包覆防止了有毒材料流出,从而该混合料还可用作建筑材料。
JP 53137222描述了对多孔材料例如炉渣提供可光固化涂层。结果改进了材料的硬度、耐热性及化学稳定性。
KR 2002001916描述了用于包裹硅石、玻璃或炉渣的可水固化涂层。该涂层由聚丙烯酸钠构成。复合材料具有好的抗海水能力。
JP 2004236546描述了碳酸钙包覆的炉渣。将具有涂层的炉渣应用于海岸或水底,据说可调节海水的pH值并减少建筑成本。
JP 7048187描述了在建筑业通过用液态树脂,特别是环氧树脂或纤维增强树脂包覆来回收利用废炉渣。
所述方案的缺点特别在于它们通常对环境影响的抵抗不足。这可能会造成涂层被破坏并使其优点不再发挥作用。
目的是对炉渣石材进行处理从而使其具有高机械稳定性并且环境友好。炉渣石材处理的方法应简单、可靠。
此目的可令人吃惊地通过用疏水性聚氨酯层包覆炉渣而实现。
本发明因而涉及疏水性聚氨酯层包覆的炉渣。
本发明还涉及生产包覆炉渣的方法,其中用疏水性聚氨酯的液态起始组分包覆炉渣,前者在炉渣表面固化。
使用的炉渣可为工业中已知的所有类型。特别是高炉渣、熔炼渣和钢厂炉渣。炉渣通常以直径在0.5~50cm范围内的碎块形式存在,优选0.5~20cm,特别优选2~15cm,特别是2.5~6.5cm。可以容许有一小部分更小碎块直至细粉尘,因其可掺入涂层中。但是粉尘的量基于炉渣不应超过10重量%,不然可能会引起聚氨酯中的扰动。
石材上的聚氨酯层通常只有几毫米厚,优选不超过5mm,特别是0.1~5mm厚。炉渣基本完全被包覆。
如上所述,炉渣的包覆通过向炉渣施加聚氨酯的液体起始组分并在其上固化来进行。可布置炉渣石材并用聚氨酯的液体起始组分将其润湿。润湿可通过例如倾倒或喷淋进行,也可通过简单的机械拌和进行,但优选喷淋。
可设计该方法以使包覆炉渣以独立碎块的形式存在。
优选地,包覆炉渣以复合体形式存在,即独立碎块通过聚氨酯彼此粘结。炉渣的独立碎块通过聚氨酯紧密粘结,粘结只在接触点发生。结果,在模塑物内部形成空穴。
复合体可通过将炉渣引入模具并向其中加入聚氨酯的液体起始组分来生产,优选通过如上所述的倾倒或喷淋进行。模具的尺寸不关键但至少应足够大从而使聚氨酯的液体起始组分可在其固化前将全部炉渣润湿。优选地,模具尺寸为100+50×100+50×15+10cm。
在本发明方法的另一实施方案中,将炉渣施加在其待用之处,例如堤、坝、堤防或交通路线,就地用聚氨酯的液体起始组分润湿,并在此处固化。
在本发明的另一实施方案中,将炉渣在拌和机中与聚氨酯的液体起始组分拌和。随后将混合料从拌和机中卸出且聚氨酯固化。
用于拌和炉渣和塑料的起始组分的拌和机原则上可以是所有类型的拌和机,只要用其可使塑料的起始组分将炉渣基本完全润湿。已证明特别适合的是包括开口容器的拌和机,例如(优选具有内件的)滚筒。为了拌和,可以旋转滚筒或者可以移动内件。
此类拌和机已公知并且用在例如建筑业中来生产混凝土混合料。
若将混合料直接施加于要固结的表面,则可有利的是将拌和机安装于车辆例如拖拉机、前端式载机或卡车上。在本发明方法的该实施方案中,在每种情况下可将混合料输送到其将要施用之处。清空拌和机后,混合料可人工分配,例如通过耙动分散。
在本发明方法的实施方案中,炉渣与聚氨酯的液体起始组分的拌和连续进行。为此,将炉渣和聚氨酯的液体起始组分连续引入拌和机中并将润湿的石材连续卸出。在此程序中,必须保证起始材料留在拌和机中直到可充分润湿炉渣。方便的是,此拌和装置可沿待固结的区段以一定速度移动,该速度使得用塑料的起始组分润湿的炉渣以固结所需的量从拌和机中卸出。也可使连续拌和装置在固定下运行,并将从拌和机中卸出的润湿炉渣输送到所需位置。
在本发明方法的连续设计的另一实施方案中,拌和机可为旋转滚筒,向其中连续引入炉渣。此滚筒装有喷嘴,其将塑料的起始组分连续分配到石材上。这里,滚筒的旋转确保了塑料和石材彻底拌和。那么,塑料/炉渣复合物通过滚筒末端的开口连续卸出。旋转滚筒可以是水平的,也可以各种角度倾斜以促进卸出。
在连续方法的另一实施方案中,将炉渣连续输送到移动穿过隧道的传送带上。隧道具有开口,塑料的起始材料经过这些开口连续卸到炉渣上。在传送带末端,炉渣落入开口拌和筒中,其以可调节的传送速度卸出复合物。
下面是关于疏水性聚氨酯的叙述。
在本发明的上下文中,聚氨酯的组分非常普遍地理解为具有自由异氰酸酯基团的化合物和具有能与异氰酸酯基团反应的基团的化合物。能与异氰酸酯基团反应的基团通常为羟基或氨基。优选羟基,因为氨基反应性非常大,反应混合物因此必须快速处理。这些组分反应形成的产物下面通称为聚氨酯。
使用的聚氨酯可以是常规的和已知的此类化合物。聚氨酯通过多异氰酸酯与有至少两个活性氢原子的化合物反应来制备。使用的多异氰酸酯原则上可以是所有多异氰酸酯、混合物和室温下为液态并且具有至少两个异氰酸酯基团的预聚物。
优选使用芳族多异氰酸酯,特别优选甲苯二异氰酸酯(TDI)的异构体和二苯基甲烷二异氰酸酯(MDI)的异构体,特别是MDI与多亚苯基多亚甲基多异氰酸酯的混合物(粗MDI)。多异氰酸酯也可以是改性的,例如通过引入异氰脲酸酯基团,特别是引入氨基甲酸酯基团改性。后提到的化合物通过使多异氰酸酯与不足化学计量的具有至少两个活性氢原子的化合物反应来制备,通常称为NCO预聚物。其NCO含量一般在2~29重量%范围内。
一般,通常将多官能醇,即所谓的多元醇或不太优选的多官能胺用作具有至少两个能与异氰酸酯基团反应的氢原子的化合物。
在本发明方法的优选实施方案中,使用的致密聚氨酯是已被赋予疏水性的那些。疏水性可特别通过向聚氨酯体系的至少一种起始组分中添加在脂肪化学中公知的羟基官能组分而产生,优选向多元醇组分中添加。
脂肪化学中公知很多羟基官能组分并可使用它们。实例为蓖麻油,羟基改性的油类如葡萄籽油、黑枯茗油、南瓜籽油、琉璃苣油、大豆油、小麦胚芽油、菜籽油、葵花油、花生油、杏仁油(apricot kernel oil)、乳香黄连木仁油、杏仁油(almond oil)、橄榄油、澳洲坚果油、鳄梨油、沙棘油、芝麻油、榛子油、月见草油、野玫瑰油、***油、红花油、胡桃油、羟基改性以及基于肉豆蔻脑酸、棕榈油酸、油酸、11-十八碳烯酸、岩芹酸、顺9-二十碳烯酸、芥酸、神经酸、亚油酸、亚麻酸、硬脂四烯酸(stearidonicacid)、花生四烯酸、二十碳五烯酸、鰶鱼酸和二十二碳六烯酸(cervonic acid)的脂肪酸酯。这里优选使用蓖麻油及其与氧化烯或酮-甲醛树脂的反应产物。后提到的化合物例如由Bayer AG以名称销售。
另外优选使用的在脂肪化学中公知的多元醇可以通过使环氧化的脂肪酸的酯开环并同时与醇反应,并且如果合适的话随后进一步酯交换反应而得到。将羟基引入油或脂肪中主要通过使这些产物中存在的烯属双键环氧化,随后使形成的环氧基团与一元羟基或多元羟基醇反应进行。从环氧化物环得到羟基或在多官能团醇情况下得到具有多个OH基的结构。由于油和脂肪一般为甘油酯,因此在上述反应情况下也发生平行的酯交换反应。如此得到的化合物优选具有在500~1500g/mol范围内的分子量。这样的产物可通过例如亨克尔反应得到。
在本发明方法的特别优选的实施方案中,使用的致密聚氨酯是可通过多异氰酸酯与具有至少两个能与异氰酸酯基团反应的氢原子的化合物反应制得的那些,其中具有至少两个活性氢原子的化合物包含至少一种脂肪化学中公知的多元醇和至少一种酚改性的芳族烃树脂,特别是茚/香豆酮树脂。这些聚氨酯及其组分具有高疏水性从而原则上甚至可在水下固化。
优选使用的具有末端酚基团的酚改性的芳族烃树脂为酚改性的茚/香豆酮树脂,特别优选芳族烃树脂的工业混合物,特别是包含通式(I)化合物的作为基本成分的那些:
(I)
其中n为2~28。此类产物可购得并且由例如Rütgers VTF AG以商品名供应。
酚改性的芳族烃树脂,特别是酚改性的茚/香豆酮树脂,通常具有0.5~5.0重量%的OH含量。
脂肪化学中公知的多元醇与酚改性的芳族烃树脂,特别是茚/香豆酮树脂优选以100∶1~100∶50的重量比使用。
可与所述化合物一起使用其他具有至少两个活性氢原子的化合物。由于聚醚醇的水解稳定性高,其是优选的。它们可通过常规公知方法制备,通常通过氧化烯与H-官能起始物质的加成反应制备。同时使用的聚醚醇优选具有至少为3的官能度和至少为400mg KOH/g,优选至少600mgKOH/g,特别是400~1000mg KOH/g的羟基值。它们以常规方式通过使至少三官能起始物质和氧化烯反应来制备。可使用的起始物质优选为分子中具有至少三个羟基的醇,如甘油、三羟甲基丙烷、季戊四醇、山梨糖醇或蔗糖。优选使用的氧化烯是氧化丙烯。
可将其他常规成分,例如催化剂和常规助剂及添加剂加入到反应混合物中。特别地,应向反应混合物中加入干燥剂,例如沸石,以避免水在组分中积累从而使聚氨酯发泡。这些物质优选添加到具有至少两个能与异氰酸酯基团反应的氢原子的化合物中。此混合物在工业上经常被称为多元醇组分。为提高复合物的长期稳定性,还有利的是加入能防止微生物侵袭的试剂。而且加入UV稳定剂有利于避免模塑物的脆化。
使用的聚氨酯原则上可在无催化剂存在下制备。为改进固化,可同时使用催化剂。选择的催化剂应优选能导致尽可能长的反应时间的那些。结果,反应混合物可长时间保持液态。如所描述,原则上也可完全无催化剂操作。
多异氰酸酯与具有至少两个能与异氰酸酯基团反应的氢原子的化合物的结合应以使异氰酸酯基团超过化学计量存在的比例进行,优选超过至少5%,特别是超过5~60%。
优选使用的疏水性聚氨酯的特点是其特别好的可加工性。因而,这些聚氨酯表现出特别好的粘合性,尤其对于潮湿的基底,如湿岩石,特别是花岗岩碎砖。尽管有水存在,聚氨酯的固化以实质上致密的形式进行。使用的致密聚氨酯甚至在薄层情况下也表现出完全致密固化。
优选使用的聚氨酯因此特别适合堤的固结,特别是坝和堤防的固结。岩石与聚氨酯之间的粘结非常强。另外,特别是在使用非常疏水的聚氨酯时,聚氨酯几乎没有水解降解,因此通过本发明方法固结的堤具有非常长的耐久性。
为实施本发明方法,优选将多异氰酸酯与具有至少两个活性氢原子的化合物混合,并将此混合物与石材拌和。原则上也可将聚氨酯的两种起始组分分开加入到石材中然后再将它们混合在一起。然而在此种情况下可能出现不均匀混合并因此造成聚氨酯的机械性能不足。
聚氨酯的起始组分可通过已知方式混合。在最简单的情况下,可将组分以所需比例引入容器,如桶中,通过简单搅拌混合,然后在拌和设备中与石材拌和。也可在聚氨酯化学中常见的混合构件,例如混合头中,混合聚氨酯的起始组分,然后使此混合物与石材接触。
通过聚氨酯的疏水处理,可抑制其水解分解。因此涂层具有几乎无限的寿命。
用疏水性聚氨酯包覆的结果是,不会有可溶的金属化合物从炉渣中释放。因此包覆的炉渣可用于所有应用,特别是用于水利工程。
根据本发明的包覆炉渣具有高强度并且可广泛使用。它既可以独立的石材形式使用,也可以复合体的形式使用。
复合体在水利工程中的优点特别是其高强度。此外,由于它们内部的空穴及因而具有的水渗透性,它们可吸收波浪的能量,从而为堤岸提供有效保护。
Claims (11)
1.被疏水性聚氨酯层包覆的包覆炉渣,其中所述炉渣的直径为0.5~50cm。
2.根据权利要求1的包覆炉渣,其中聚氨酯层的厚度不超过5mm。
3.根据权利要求1的包覆炉渣,其中聚氨酯层的厚度为0.1~5mm。
4.根据权利要求1的包覆炉渣,其中炉渣颗粒通过聚氨酯粘结得到模塑物。
5.根据权利要求1的包覆炉渣,其中聚氨酯的制备通过使多异氰酸酯与具有至少两个活性氢原子的化合物反应来进行。
6.根据权利要求5的包覆炉渣,其中具有至少两个活性氢原子的化合物包含至少一种在脂肪化学中已知的羟基官能组分。
7.根据权利要求5的包覆炉渣,其中具有至少两个活性氢原子的化合物包含至少一种酚改性的茚/香豆酮树脂。
8.一种生产包覆炉渣的方法,其中用疏水性聚氨酯的液态起始组分润湿炉渣,前者在炉渣表面上固化,其中所述炉渣的直径为0.5~50cm。
9.根据权利要求8的方法,其中通过喷淋用疏水性聚氨酯的液态起始组分润湿炉渣。
10.根据权利要求8的方法,其中通过倾倒用疏水性聚氨酯的液态起始组分润湿炉渣。
11.根据权利要求8的方法,其中在拌和机中用疏水性聚氨酯的液态起始组分润湿炉渣。
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PCT/EP2006/067066 WO2007042451A1 (de) | 2005-10-10 | 2006-10-05 | Beschichtete schlacke |
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DE102009058101A1 (de) * | 2009-12-12 | 2011-06-16 | Bayer Materialscience Ag | Verwendung von Schichtaufbauten in Windkraftanlagen |
US8329455B2 (en) | 2011-07-08 | 2012-12-11 | Aikan North America, Inc. | Systems and methods for digestion of solid waste |
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US4142555A (en) * | 1976-01-19 | 1979-03-06 | Sumitomo Kinzoku Kogyo Kabushiki Kaisha | Corrosion preventive, coated metal pipe |
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US20080257108A1 (en) | 2008-10-23 |
WO2007042451A1 (de) | 2007-04-19 |
EP1940986A1 (de) | 2008-07-09 |
CN101283064A (zh) | 2008-10-08 |
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