CN112874059A - 一种低成本炼化管道用耐蚀耐热复合板及其制造方法 - Google Patents
一种低成本炼化管道用耐蚀耐热复合板及其制造方法 Download PDFInfo
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Abstract
本发明提供了一种低成本炼化管道用耐蚀耐热复合板及其制造方法,所述复合板依次由基板、耐热板、耐蚀板三层钢板复合而成,制造方法为坯料设计—复板制备—复板与基板组坯—真空封焊—复合板坯轧制—固溶处理—分板—回火处理;应用本发明生产的复合板综合性能优异,结合率达到100%;钢板超声检测结果100%满足NB/T47013.3Ⅰ级;不仅具有耐蚀、耐热双层特性,而且在复合层厚度上进行减薄,在延长设备使用寿命的同时,极大地降低了设备的制作成本。
Description
技术领域
本发明属于金属材料领域,尤其涉及一种低成本炼化管道用耐蚀耐热复合板及其制造方法。
背景技术
双金属、多层金属复合材料是将两种或多种不同金属材料通过一定工艺、技术复合而成以发挥其不同技术特性的材料。其兼有基体钢板和复层材料的双重或多重优点,相对于纯不锈钢或合金能有效降低成本,且具有不锈钢或合金等抗应力腐蚀、耐酸性及耐高温等综合特性。它能最大限度地实现材料的优势互补,节省合金元素,降低工程费用及维护成本,同时不降低安全性。
近年来,国内外油气田开发及炼化难度日益增加,工况条件日益苛刻,高温,高压,高含CO2、H2S、Cl-及元素硫等油气的相继出现,是传统单一的耐蚀材料和防腐技术已不能满足油气开采及炼化需求,因此对新材料特别是双金属、多层金属复合材料的需求日益迫切。本发明之前,专利CN109306436A公开了“一种具有耐腐蚀性的抗酸管线用复合板及其制造方法”,该发明以制造抗酸性管线钢为目的,选择耐蚀性优异的奥氏体不锈钢作为耐蚀层,但由于接触环境为常温,复合材料不具备耐高温性能。
本发明之前,发明《一种耐磨耐热双金属复合板及其制备方法》(CN 1109652743A)公开了的耐热双金属复合板实现材料的耐磨性同时兼顾耐热性,耐热材料选择低合金钢材质,耐热效果不如奥氏体不锈钢,钢质无耐蚀性,另外工艺上采用添加钎料复合焊接方式对复合界面结合效果较差。
发明《一种适于高温工况的耐磨耐腐蚀复合板》(CN 103192161A)公开的复合板添加了大量的Cr、Mo、W、B元素,使复合板具有较高的耐磨性、耐蚀性,但由于是采用焊丝在基板上堆焊的工艺,存在堆焊不均匀的问题,影响堆焊层组织均匀性,不利于复合板的耐蚀性能。
发明《一种耐热耐磨复合板及其制造方法》(CN 103342020A)公开的技术方案中采用奥氏体耐热不锈钢和耐磨钢结合的方式,达到耐热耐磨效果,但耐热层奥氏体不锈钢厚度较厚,导致成本高昂。
因此,为解决上述问题,本发明意在提供一种低成本炼化管道用耐蚀耐热复合板及其制造方法,解决在高温、腐蚀环境中使用的双重复合的材料复层不锈钢较厚,成本高的问题,开发的耐蚀耐热复合板不仅结合效果优异、具有优异的耐高温性能和耐蚀性,在保证设备的使用寿命同时,有效降低制造成本。
发明内容
本发明的目的在于克服上述问题和不足而提供一种结合效果优异,兼具耐热、耐蚀双重特性,解决炼化设备及管道在长期高温、强腐蚀环境下引起使用寿命降低的潜在风险问题,确保设备安全生产运营的低成本炼化管道用耐蚀耐热复合板及其制造方法。
本发明目的是这样实现的:
一种低成本炼化管道用耐蚀耐热复合板,所述复合板依次由基板、芯层耐热板、外层耐蚀板三层钢板复合而成。
所述外层基板的成分按重量百分比含有:C 0.12%~0.15%、Si 0.30%~0.45%、Mn 0.50%~0.60%、P≤0.010%、S≤0.005%、Cr 1.00%~1.50%、Mo 0.30%~0.60%、Nb 0.020%~0.050%,其余为Fe及不可避免杂质。
所述中间耐热板的成分按重量百分比含有:C 0.04%~0.06%、Si 0.90%~1.05%、Mn 0.90%~1.05%、P≤0.020%、S≤0.005%、Cr 23.0%~26.0%、Ni 19.0%~22.0%、Mo 2.0%~4.0%,其余为Fe及不可避免杂质。
所述表层耐蚀板的成分按重量百分比含有:C 0.02%~0.04%、Si 0.55%~0.65%、Mn 1.00%~1.15%、P≤0.020%、S≤0.005%、Cr 17.0%~19.0%、Ni 9.0%~13.0%、Ti 0.30%~1.00%,其余为Fe及不可避免杂质。
所述复合板的厚度为13~26mm,其中外层基板的厚度为10~20mm,芯层耐热板的厚度为1~2mm,外层层耐蚀板的厚度为2~4mm。
本发明复合板中外层基板的成分设计理由如下:
C:C是钢中的必不可少的强化元素,在固溶强化和析出强化过程中起到提高强度的作用,但过高的C含量对塑韧性和焊接不利,因此本发明将C含量范围设定在0.12%~0.15%。
Si:加入Si是为了炼钢过程中脱氧与提高机体的强度,Si还有抑制渗碳体形成的作用。如果添加过量的Si,母材及其焊接热影响区的韧性就会显著降低,因此本发明将Si含量范围设定在0.20%~0.45%。
Mn:Mn是良好的脱氧剂和脱硫剂。提高Mn的含量,钢的淬透性增加,含量增加到一定程度后,会导致焊接性能下降尤其是严重恶化焊接热影响区的韧性,另外,过高的Mn含量还会增加连铸坯中心偏析,使钢板性能的各项异性增加,因此本发明将Mn含量范围设定在0.50%~0.60%。
P、S:是钢中不可避免的杂质元素,尽量越低越好,但出于成本考虑,又不能无限制的低,因此本发明将P、S含量上限分别设定为0.010%、0.005%。
Cr:铬是强碳化物形成元素,同时具有较高的淬透性,能够显著提高反应器壳体钢板的室温强度及中温强度,因此本发明将Cr含量控制在1.00%~1.50%;
Mo:钼在钢中的作用是提高淬透性和热强性,防止回火脆性,因此本发明将Mo含量控制在0.30%~0.60%;
Nb:钒能细化钢的晶粒,提高钢的强度、低温韧性,改善钢的焊接性能及模拟焊后热处理性能,同时钒对碳的固定作用,还可以提高钢在高温下的抗氢侵蚀。因此本发明将Nb含量控制在0.020%~0.050%;
本发明复合板中中间耐热板的成分设计理由如下:
C:C是钢中的必不可少的强化元素,通过固溶作用和与铬结合形成碳化物起到析出强化作用增强基体强度,但C含量过高对其耐蚀性有不利影响,因此本发明将C含量范围设定在0.04%~0.06%。
Si:加入Si是为了炼钢过程中脱氧与提高机体的强度,Si还有抑制渗碳体形成的作用。如果添加过量的Si,容易形成硅的碳化对高温持久性能不利,因此本发明将Si含量范围设定在0.90%~1.05%。
Mn:Mn是良好的脱氧剂和脱硫剂,起到固溶强化的作用的同时具有强烈的稳定奥氏体作用,因此本发明将Mn含量范围设定在0.90%~1.05%。
P、S:是钢中不可避免的杂质元素,尽量越低越好,但出于成本考虑,又不能无限制的低,因此本发明将P、S含量上限分别设定为0.020%、0.005%。
Cr:含量超过12%时。使钢有良好的高温抗氧化性和耐氧化性介质腐蚀的作用。还增加钢的热强性,铬为不锈耐酸钢及耐热钢的主要合金元素。铬能提高碳素钢轧制状态的强度和硬度,降低伸长率和断面收缩率。当铬含量超过15%时,强度和硬度将下降,伸长率和断面收缩率则相应地有所提高。含铬钢的零件经研磨容易获得较高的表面加工质量,因此本发明将Cr含量控制在23.0%~26.0%;
Ni:镍主要提高钢的耐蚀性,形成奥氏体组织,同时与Ni配合提高钢的性能,因此本发明将Ni含量控制在9.0%~13.0%;
Mo:钼在钢中的作用是提高热强性和热稳定性,因此本发明将Mo含量控制在2.00%~4.00%;
本发明复合板中外层耐蚀板的成分设计理由如下:
C:C是钢中的必不可少的强化元素,通过固溶作用和与铬结合形成碳化物起到析出强化作用增强基体强度,但C含量过高对其耐蚀性有不利影响,因此本发明将C含量范围设定在0.02%~0.04%。
Si:加入Si是为了炼钢过程中脱氧与提高机体的强度,Si还有抑制渗碳体形成的作用。如果添加过量的Si,容易形成硅的碳化对高温持久性能不利,因此本发明将Si含量范围设定在0.55~0.65%。
Mn:Mn是良好的脱氧剂和脱硫剂,起到固溶强化的作用的同时具有强烈的稳定奥氏体作用,因此本发明将Mn含量范围设定在1.00%~1.15%。
P、S:是钢中不可避免的杂质元素,尽量越低越好,但出于成本考虑,又不能无限制的低,因此本发明将P、S含量上限分别设定为0.020%、0.005%。
Cr:耐蚀层添加铬,主要发挥铬的耐蚀性特性,在氧化介质中,使钢表面形成一层牢固而致密的铬的氧化物,保护钢板基体;铬溶于钢中能显著提高钢的电极电位,降低了因电极电位不同形成的电化学腐蚀,铬与镍结合,可形成单相奥氏体组织并使钢具有良好的耐蚀性、强韧性,因此本发明将Cr含量控制在17.0%~19.0%;
Ni:镍主要提高钢的耐蚀性,形成奥氏体组织,同时与Ni配合提高钢的性能,因此本发明将Ni含量控制在9.0%~13.0%;
Ti:钢中稳定C元素,提高不锈钢的各种形式的腐蚀性能,因此本发明将Nb含量控制在0.30%~1.00%;
本发明技术方案之二是提供一种低成本炼化管道用耐蚀耐热复合板的制造方法,其工艺路线为:坯料设计—复板制备—复板与基板组坯—真空封焊—复合板坯轧制—热处理—分板—回火处理;
(1)坯料设计:外层基板坯料厚度60~120mm、芯层耐热板坯料厚度30~60mm、外层耐蚀板坯料厚度50~100mm;
(2)复板制备:
复板由芯层耐热板和外层耐蚀板组坯后轧制而成;具体为:
芯层耐热钢坯和外层耐蚀钢坯对齐叠放,采用焊接方式将二者四周进行封焊,之后进行真空封焊,预留直径5mm~10mm小孔用于排除接触层空气,通过真空泵抽真空处理,使结合层真空度达到1×10-2Pa~5×10-2Pa,将孔洞封焊,组坯厚度为80mm~160mm;之后在1180℃~1230℃保温3h~4h,均匀烧透,进行高温轧制,开轧温度1100℃~1150℃,终轧温度950℃~1050℃,轧后进行热矫直,保证钢板的平直度,轧制后的钢板作为复板待用;复板的厚度规格为15~30mm;复板中耐热板厚度为5~10mm,耐蚀板厚度为10~20mm;
(3)复板与基板组坯:
复板四周焊接不锈钢金属边框,高度与待复合的基板厚度相同,边框厚度5mm~10mm,基板置入金属边框内,基板与边框的间隙<5mm,基板与复板的接触面为芯层耐热板,形成复合板板坯;
将两块复合板板坯对称叠放;形成由上而下分别为复板-基板-基板-复板的坯料,其中,两块基板之间均匀布置隔离剂,将上下金属边框进行密闭封焊;
(4)真空封焊:在金属边框中心处钻取直径5~10mm小孔用于排除复合层中间气体,采用真空泵进行抽真空处理,真空度达到1×10-2Pa~5×10-2Pa,然后将孔洞封焊;
(5)复合板坯轧制:复板与基板组坯后坯料的在1150℃~1250℃保温15min/cm~25min/cm,使得坯料均匀烧透,在此期间使结合界面的金属原子充分扩散融合,同时使界面处的及少量残余气体充分外排;然后采用大轧制力进行轧制,前三个道次压下率总和20%~30%,由于复合层较薄且与轧辊直接接触,大的轧制力通过复层渗透至复层与基层的结合处,使二者充分塑性变形,使基层与复层结合界面形成原子间结合,复合轧后的两组对称复合板的总厚度为26mm~52mm,具有优异的表面质量和板型;
(6)热处理:热处理温度1030℃~1060℃,保温10min~30min,水冷至900℃~930℃后空冷至室温。
(7)分板:对称复合板采用等离子切割方式沿钢板长度方向切割,分板得到两组三层耐蚀耐热复合板,复合板厚度为13~26mm;具体为外层基板厚度为10~20mm,芯层耐热板厚度为1~2mm,外层耐蚀板厚度为2~4mm;
(8)回火处理:回火温度为700℃~750℃,保温1.0min/mm~3.0min/mm,经热处理后钢板具有良好的综合性能。
进一步,所述步骤(2)中,芯层耐热板和外层耐蚀板组坯前对其接触表面清理加工,去除锈层,露出新鲜光亮的金属,对金属表面进行除油污处理,防止因表面异物影响结合效果。
进一步,所述步骤(3)复板与基板组坯前,对复板的六个面进行清理加工,除去黑皮,露出新鲜光亮的金属,对金属表面进行除油污处理,防止因表面异物影响结合效果。
本发明的有益效果在于:
(1)可以生产板型、表面质量优异,包括外层基板(10mm~20mm)+芯层耐热板(1mm~2mm)+外层耐蚀版(2mm~4mm)的三层耐蚀耐热复合板;
(2)开发的复合板综合性能优异,基板室温Rel≥310MPa、510≤Rm≤620MPa、30%≤A50≤40%、150≤HV≤170,耐蚀层与耐热层、耐热层与基层的剪切强度≥360MPa,由于耐热层添加了提高热强性的Cr、Ni、Mo等合金元素表现出优异的热强性和高温抗氧化性,耐蚀层添加了Cr、Ni、Ti等合金元素表现出优异耐蚀性,按GB/T 4334 E法进行的晶间腐蚀试验合格;
(3)本发明的制造的复合板结合率达到100%;钢板超声检测结果100%满足NB/T47013.3 Ⅰ级。与传统的双层复合板相比,本发明采用的不同成分的耐蚀层和耐热层材质钢板,不仅具有耐蚀、耐热双层特性,而且在复合层厚度上进行减薄,在延长设备使用寿命的同时,极大地降低了设备的制作成本。
具体实施方式
下面通过实施例对本发明作进一步的说明。
本发明实施例根据技术方案的组分配比,进行坯料设计—复板制备—复板与基板组坯—真空封焊—复合板坯轧制—三层复合组坯加热轧制—热处理—分板—回火处理。
(1)坯料设计:外层基板坯料厚度60~120mm、芯层耐热板坯料厚度30~60mm、外层耐蚀板坯料厚度50~100mm;
(2)复板制备:
复板由芯层耐热板和外层耐蚀板组坯后轧制而成;具体为:
芯层耐热钢坯和外层耐蚀钢坯对齐叠放,进行真空封焊,组坯厚度为80~160mm;之后在1180~1230℃保温3~4h后进行高温轧制,开轧温度1100~1150℃,终轧温度950~1050℃,轧后进行热矫直,轧制后的钢板作为复板待用;复板的厚度为15~30mm,其中复板中耐热板的厚度为5~10mm,耐蚀板的厚度为10~20mm;
(3)复板与外层基板组坯:
复板四周焊接不锈钢金属边框,高度与待复合的基板厚度相同,边框厚度5~10mm,基板置入金属边框内,基板与边框的间隙<5mm,基板与复板的接触面为芯层耐热板,形成复合板板坯;
将两块复合板板坯对称叠放;形成由上而下分别为复板-基板-基板-复板的坯料,其中,两块基板之间均匀布置隔离剂,将上下金属边框进行密闭封焊,之后进行真空封焊;
(4)轧制:加热至1150℃~1250℃保温15~25min/cm;然后采用大轧制力进行轧制,前三个道次压下率总和20%~30%;
(5)热处理:热处理温度1030~1060℃,保温10~30min,水冷至900~930℃后空冷至室温;
(6)分板:采用等离子切割方式沿钢板长度方向切割,分板得到两组三层耐蚀耐热复合板;
(7)回火处理:回火温度为700~750℃,保温1.0~3.0min/mm,经热处理后钢板具有良好的综合性能;
进一步;所述步骤(2)中,芯层耐热板和外层耐蚀板组坯前对其接触表面清理加工,去除锈层,露出新鲜光亮的金属,对金属表面进行除油污处理。
进一步;所述步骤(3)复板与基板组坯前,对复板的六个面进行清理加工,除去黑皮,露出新鲜光亮的金属,对金属表面进行除油污处理。
进一步;所述真空封焊为在金属边框中心处钻取直径5~10mm小孔用于排除复合层中间气体,采用真空泵进行抽真空处理,真空度达到1×10-2~5×10-2Pa,然后将孔洞封焊。
本发明实施例钢的成分见表1。本发明实施例钢的主要工艺参数见表2。本发明实施例钢的性能见表3。本发明实施例钢内外部质量见表4。本发明实施例钢抗高温高压下抗SCC性能见表5。本发明实施例钢腐蚀性能见表6。
表1本发明实施例钢的成分(wt%)
表2本发明实施例钢的主要工艺参数
表3本发明实施例钢的性能
表4发明实施例钢内外部质量
表5本发明实施例钢抗高温高压下抗SCC性能
实施例 | 在温度为200℃、压力为0.17MPa的试验条件下,试验720小时 |
1 | 未断裂 |
2 | 未断裂 |
3 | 未断裂 |
4 | 未断裂 |
5 | 未断裂 |
6 | 未断裂 |
表6本发明钢耐腐蚀性能
为了表述本发明,在上述中通过实施例对本发明恰当且充分地进行了说明,以上实施方式仅用于说明本发明,而并非对本发明的限制,有关技术领域的普通技术人员,在不脱离本发明的精神和范围的情况下,还可以做出各种变化和变型,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内,本发明的专利保护范围应由权利要求限定。
Claims (9)
1.一种低成本炼化管道用耐蚀耐热复合板,其特征在于,所述复合板依次由基板、耐热板、耐蚀板三层钢板复合而成。
2.根据权利要求1所述的一种低成本炼化管道用耐蚀耐热复合板,其特征在于,所述基板的成分按重量百分比含有:C 0.12%~0.15%、Si 0.30%~0.45%、Mn 0.50%~0.60%、P≤0.010%、S≤0.005%、Cr 1.00%~1.50%、Mo 0.30%~0.60%、Nb 0.020%~0.050%,其余为Fe及不可避免杂质。
3.根据权利要求1所述的一种低成本炼化管道用耐蚀耐热复合板,其特征在于,所述中间耐热板的成分按重量百分比含有:C 0.04%~0.06%、Si 0.90%~1.05%、Mn 0.90%~1.05%、P≤0.020%、S≤0.005%、Cr 23.0%~26.0%、Ni 19.0%~22.0%、Mo 2.0%~4.0%,其余为Fe及不可避免杂质。
4.根据权利要求1所述的一种低成本炼化管道用耐蚀耐热复合板,其特征在于,所述表层耐蚀板的成分按重量百分比含有:C 0.02%~0.04%、Si 0.55%~0.65%、Mn 1.00%~1.15%、P≤0.020%、S≤0.005%、Cr 17.0%~19.0%、Ni 9.0%~13.0%、Ti 0.30%~1.00%,其余为Fe及不可避免杂质。
5.根据权利要求1所述的一种低成本炼化管道用耐蚀耐热复合板,其特征在于,所述复合板的厚度为13~26mm,其中外层基板的厚度为10~20mm,芯层耐热板的厚度为1~2mm,外层层耐蚀板的厚度为2~4mm。
6.一种权利要求1—5任一项所述的一种低成本炼化管道用耐蚀耐热复合板的制备方法,包括坯料设计—复板制备—复板与基板组坯—真空封焊—复合板坯轧制—三层复合组坯加热轧制—热处理—分板—回火处理;其特征在于:
(1)坯料设计:外层基板坯料厚度60~120mm、芯层耐热板坯料厚度30~60mm、外层耐蚀板坯料厚度50~100mm;
(2)复板制备:
复板由芯层耐热板和外层耐蚀板组坯后轧制而成;具体为:
芯层耐热钢坯和外层耐蚀钢坯对齐叠放,进行真空封焊,组坯厚度为80~160mm;之后在1180~1230℃保温3~4h后进行高温轧制,开轧温度1100~1150℃,终轧温度950~1050℃,轧后进行热矫直,轧制后的钢板作为复板待用;复板的厚度为15~30mm,其中复板中耐热板的厚度为5~10mm,耐蚀板的厚度为10~20mm;
(3)复板与外层基板组坯:
复板四周焊接不锈钢金属边框,高度与待复合的基板厚度相同,边框厚度5~10mm,基板置入金属边框内,基板与边框的间隙<5mm,基板与复板的接触面为芯层耐热板,形成复合板板坯;
将两块复合板板坯对称叠放;形成由上而下分别为复板-基板-基板-复板的坯料,其中,两块基板之间均匀布置隔离剂,将上下金属边框进行密闭封焊,之后进行真空封焊;
(4)轧制:加热至1150~1250℃保温15~25min/cm;然后采用大轧制力进行轧制,前三个道次压下率总和20%~30%;
(5)热处理:热处理温度1030~1060℃,保温10~30min,水冷至900~930℃后空冷至室温;
(6)分板:采用等离子切割方式沿钢板长度方向切割,分板得到两组三层耐蚀耐热复合板;
(7)回火处理:回火温度为700~750℃,保温时间1.0~3.0min/mm。
7.根据权利要求6所述的一种低成本炼化管道用耐蚀耐热复合板的制备方法,其特征在于,所述步骤(2)中,芯层耐热板和外层耐蚀板组坯前对其接触表面清理加工,去除锈层,露出新鲜光亮的金属,对金属表面进行除油污处理。
8.根据权利要求6所述的一种低成本炼化管道用耐蚀耐热复合板的制备方法,其特征在于,所述步骤(3)复板与基板组坯前,对复板的六个面进行清理加工,除去黑皮,露出新鲜光亮的金属,对金属表面进行除油污处理。
9.根据权利要求6所述的一种低成本炼化管道用耐蚀耐热复合板的制备方法,其特征在于,所述真空封焊为在金属边框中心处钻取直径5~10mm小孔用于排除复合层中间气体,采用真空泵进行抽真空处理,真空度达到1×10-2~5×10-2Pa,然后将孔洞封焊。
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