WO2020140317A1 - 难热解材料的挥发分释放特性指数计算方法 - Google Patents

难热解材料的挥发分释放特性指数计算方法 Download PDF

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WO2020140317A1
WO2020140317A1 PCT/CN2019/076219 CN2019076219W WO2020140317A1 WO 2020140317 A1 WO2020140317 A1 WO 2020140317A1 CN 2019076219 W CN2019076219 W CN 2019076219W WO 2020140317 A1 WO2020140317 A1 WO 2020140317A1
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weight loss
pyrolyze
materials
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徐青伟
许开立
陈守坤
葛及
徐晓虎
姚锡文
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Northeastern University China
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    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N5/00Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
    • G01N5/04Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder

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  • the invention relates to the technical field of pyrolysis, in particular to a method for calculating the volatile content release index of difficult pyrolysis materials.
  • the Volatile Release Characteristics Index reflects the volatile analysis characteristics of the material. The larger the value, the better the volatile analysis characteristics of the material and the easier the pyrolysis reaction.
  • the initial precipitation temperature of volatile matter needs to be determined first, and the corresponding weight loss rate of the material should reach 0.1 mg/min; when performing thermogravimetric analysis experiments, the mass of the experimental sample is usually 5 mg, thus The weight loss rate of the material is required to reach 2 wt%/min (wt% means weight percentage).
  • coal, biomass wood, peanut husk, rice husk, corn cob
  • sludge and other easily pyrolyzed materials their volatile content is high and pyrolysis is easy to occur at high temperature, for example, the volatile content of biomass and other materials
  • the content is as high as 70wt%, and the weight loss rate is relatively easy to reach 2wt%/min, so that the volatile content release index can be calculated according to the concept.
  • difficult pyrolysis materials with a weight loss rate of less than 2wt%/min during the heating process such as the molding sand widely used in the foundry industry, their volatile content is low and pyrolysis is difficult to occur at high temperatures.
  • the present invention provides a method for calculating the volatile content release index of hard-to-pyrolyze materials, which can calculate the volatile content release index of materials, especially hard-to-pyrolyze materials.
  • the high performance is conducive to the further analysis of the material pyrolysis characteristics.
  • a method for calculating the volatile content release index of difficult-to-pyrolyze materials characterized in that it includes the following steps:
  • Step 4 Analyze the remaining mass percentage data at each temperature and the volatile weight loss rate data obtained at each time in steps 1 and 2 to determine the weight loss rate m loss of difficult-to-pyrolyze materials.
  • Maximum weight loss rate (dw/dt) max , average volatile weight loss rate (dw/dt) mean and temperature corresponding to the maximum volatile weight loss rate T max , half-peak width ie (dw/dt)/(dw/dt) max The temperature range at 1/2 is ⁇ 1/2 ; where the units of T s , T max and ⁇ 1/2 are °C, and the units of (dw/dt) max and (dw/dt) mean are w
  • Step 5 Calculate the volatile release index of refractory materials
  • the unit of D is wt% 2 /min 2 /°C 3 .
  • the present invention can calculate the volatile content release index of difficult-to-pyrolyze materials, and is also suitable for solving the volatile content release index of general materials, which expands the volatile content release characteristics. Application areas of the index.
  • the present invention can provide an idea for the study of the thermal stability of materials by calculating the volatile content release index of difficult-to-pyrolyze materials.
  • FIG. 1 is a flowchart of a method for calculating the volatile content release index of a hard-to-pyrolyze material of the present invention
  • FIG. 2 is a graph showing the thermal weight loss curves of the foundry sands of steel castings in the first, second, and third embodiments of the method for calculating the volatile content release index of the hard-to-pyrolyze materials of the present invention.
  • the object of the present invention is to provide a method for calculating the volatile content release index of hard-to-pyrolyze materials, which can calculate the volatile content release index of materials, especially hard-to-pyrolyze materials. Further analysis of material pyrolysis characteristics.
  • FIG. 1 it is a flowchart of a method for calculating the volatile content release index of the hard-to-pyrolyze material of the present invention.
  • FIG. 2 it is the thermal weightlessness curve graph of the casting sand of the steel castings in the first, second and third embodiments of the present invention under different heating rates.
  • the method for calculating the volatile content release index of the hard-to-pyrolyze material of the present invention includes the following steps:
  • Step 5 Calculate the volatile release index of refractory materials
  • the weight loss rate of the hard-to-pyrolyze material m loss 0.98%
  • the weight loss rate of the hard-to-pyrolyze material m loss 1.36%

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Abstract

一种难热解材料的挥发分释放特性指数计算方法,首先获取难热解材料在一定升温速率时每一温度下的剩余质量百分比数据,形成热失重曲线;然后对热失重曲线进行分析,得到每一时刻的挥发分失重速率数据;接着定义关于挥发分初始析出速率与失重率的阈值;然后确定失重率,计算挥发分初始析出速率,从而确定挥发分初始析出速率对应的挥发分初始析出温度,并确定难热解材料的挥发分最大失重速率、挥发分平均失重速率及挥发分最大失重速率对应的温度、半峰宽;最后根据上述数据计算得到难热解材料的挥发分释放特性指数。本方法能够对材料尤其是难热解材料的挥发分释放特性指数进行计算,计算结果准确性及可靠性高。

Description

难热解材料的挥发分释放特性指数计算方法 技术领域
本发明涉及热解技术领域,特别是涉及一种难热解材料的挥发分释放特性指数计算方法。
背景技术
挥发分释放特性指数反应了材料的挥发分析出特性,其值越大,表明材料的挥发分析出特性越好,热解反应越容易进行。
现有的挥发分释放特性指数计算方法中,需要首先确定挥发分初始析出温度,对应的材料失重速率应达到0.1mg/min;在进行热重分析实验时,实验样品的质量通常为5mg,从而需要材料的失重速率达到2wt%/min(wt%表示重量百分比)。对于煤炭、生物质(木材、花生壳、稻壳、玉米芯)、污泥等易热解材料,其挥发分含量高且在高温状态下容易发生热解,例如,生物质等材料的挥发分含量高达70wt%,其失重速率比较容易达到2wt%/min,从而能够按照概念对其挥发分释放特性指数进行计算。而对于在升温过程中失重速率小于2wt%/min的难热解材料,例如在铸造行业中广泛使用的型砂,其挥发分含量低且在高温状态下很难发生热解,若严格按照概念,将无法计算出其挥发分释放特性指数,从而不能对难热解材料的热解特性进行比较分析。可见,现有的挥发分释放特性指数计算方法不适用于难热解材料,关于难热解材料的挥发分释放特性指数的计算成为一个难题。
发明内容
针对现有技术存在的问题,本发明提供一种难热解材料的挥发分释放特性指数计算方法,能够对材料尤其是难热解材料的挥发分释放特性指数进行计算,计算结果准确性及可靠性高,有利于对材料热解特性的进一步分析。
本发明的技术方案为:
一种难热解材料的挥发分释放特性指数计算方法,其特征在于,包括下述步骤:
步骤1:获取难热解材料在升温速率为β时每一温度下的剩余质量百分比W,形成热失重曲线W=f(T);其中,W为难热解材料的剩余质量百分比,T为温度,T=β×t,t为难热解材料的加热时间;W、T、β、t的单位分别为wt%、℃、℃/min、min;
步骤2:对难热解材料的热失重曲线进行分析,得到每一时刻的挥发分失重速率dw/dt;其中,w为难热解材料的挥发分质量百分比,w=1-W,从而dw/dt=-β×dW/dT,w、dw/dt、 dW/dT的单位分别为wt%、wt%/min、wt%/℃;
步骤3:定义阈值
Figure PCTCN2019076219-appb-000001
其中,T v为难热解材料的挥发分初始析出速率,m loss为难热解材料的失重率;f的值为定值,用2wt%/min的挥发分初始析出速率与生物质能源的70%的失重率来衡量,从而f=2.86wt%/min;
步骤4:对所述步骤1和步骤2中得到的每一温度下的剩余质量百分比数据及每一时刻的挥发分失重速率数据进行分析,确定难热解材料的失重率m loss,计算得到难热解材料的挥发分初始析出速率T v=f×m loss,从而确定当挥发分失重速率dw/dt=T v时对应的挥发分初始析出温度T s,并确定难热解材料的挥发分最大失重速率(dw/dt) max、挥发分平均失重速率(dw/dt) mean及挥发分最大失重速率对应的温度T max、半峰宽即(dw/dt)/(dw/dt) max=1/2时的温度区间Δ 1/2;其中,T s、T max、Δ 1/2的单位均为℃,(dw/dt) max、(dw/dt) mean的单位均为wt%/min;
步骤5:计算得到难热解材料的挥发分释放特性指数
Figure PCTCN2019076219-appb-000002
其中,D的单位为wt% 2/min 2/℃ 3
本发明的有益效果为:
本发明与现有的挥发分释放特性指数计算方法相比,能够计算出难热解材料的挥发分释放特性指数,也适用于一般材料的挥发分释放特性指数的求解,拓展了挥发分释放特性指数的应用领域。本发明通过计算难热解材料的挥发分释放特性指数,能够为材料热稳定性的研究提供一种思路。
附图说明
图1为本发明的难热解材料的挥发分释放特性指数计算方法的流程图;
图2为本发明的难热解材料的挥发分释放特性指数计算方法的实施例一、二、三中铸钢件型砂在不同升温速率下的热失重曲线图。
具体实施方式
下面将结合附图和具体实施方式,对本发明作进一步描述。
本发明的目的是提供一种难热解材料的挥发分释放特性指数计算方法,能够对材料尤其是难热解材料的挥发分释放特性指数进行计算,计算结果准确性及可靠性高,有利于对材料 热解特性的进一步分析。
如图1所示,为本发明的难热解材料的挥发分释放特性指数计算方法的流程图。如图2所示,为本发明的实施例一、二、三中铸钢件型砂在不同升温速率下的热失重曲线图。
实施例一
本发明的难热解材料的挥发分释放特性指数计算方法,包括下述步骤:
步骤1:获取难热解材料在升温速率为β时每一温度下的剩余质量百分比W,形成热失重曲线W=f(T);其中,W为难热解材料的剩余质量百分比,T为温度,T=β×t,t为难热解材料的加热时间;W、T、β、t的单位分别为wt%、℃、℃/min、min。
本实施例一中,难热解材料为铸钢件型砂,升温速率β=20℃/min,图2中的曲线a为铸钢件型砂在氮气氛围下升温速率β=20℃/min时的热失重曲线。
步骤2:对难热解材料的热失重曲线进行分析,得到每一时刻的挥发分失重速率dw/dt;其中,w为难热解材料的挥发分质量百分比,w=1-W,从而dw/dt=-β×dW/dT,w、dw/dt、dW/dT的单位分别为wt%、wt%/min、wt%/℃。
步骤3:定义阈值
Figure PCTCN2019076219-appb-000003
其中,T v为难热解材料的挥发分初始析出速率,m loss为难热解材料的失重率;f的值为定值,用2wt%/min的挥发分初始析出速率与生物质能源的70%的失重率来衡量,从而f=2.86wt%/min。
步骤4:对所述步骤1和步骤2中得到的每一温度下的剩余质量百分比数据及每一时刻的挥发分失重速率数据进行分析,确定难热解材料的失重率m loss=0.83%,计算得到难热解材料的挥发分初始析出速率T v=f×m loss=2.37×10 -2wt%/min,从而确定当挥发分失重速率dw/dt=T v时对应的挥发分初始析出温度T s=152℃,并确定难热解材料的挥发分最大失重速率(dw/dt) max=4.54×10 -2wt%/min、挥发分平均失重速率(dw/dt) mean=1.56×10 -2wt%/min及挥发分最大失重速率对应的温度T max=464℃、半峰宽即(dw/dt)/(dw/dt) max=1/2时的温度区间Δ 1/2=450℃。
步骤5:计算得到难热解材料的挥发分释放特性指数
Figure PCTCN2019076219-appb-000004
实施例二
本实施例二与上述实施例一的区别在于,升温速率β=30℃/min,图2中的曲线b为铸钢件型砂在氮气氛围下升温速率β=30℃/min时的热失重曲线。
本实施例二中,难热解材料的失重率m loss=0.98%,计算得到难热解材料的挥发分初始析出速率T v=f×m loss=2.80×10 -2wt%/min,从而确定当挥发分失重速率dw/dt=T v时对应的挥发分初始析出温度T s=115℃、难热解材料的挥发分最大失重速率(dw/dt) max=6.58×10 -2wt%/min、挥发分平均失重速率(dw/dt) mean=2.76×10 -2wt%/min及挥发分最大失重速率对应的温度T max=473℃、半峰宽即(dw/dt)/(dw/dt) max=1/2时的温度区间Δ 1/2=483℃。计算得到难热解材料的挥发分释放特性指数
Figure PCTCN2019076219-appb-000005
实施例三
本实施例三与上述实施例一的区别在于,升温速率β=40℃/min,图2中的曲线c为铸钢件型砂在氮气氛围下升温速率β=40℃/min时的热失重曲线。
本实施例三中,难热解材料的失重率m loss=1.36%,计算得到难热解材料的挥发分初始析出速率T v=f×m loss=3.89×10 -2wt%/min,从而确定当挥发分失重速率dw/dt=T v时对应的挥发分初始析出温度T s=126℃、难热解材料的挥发分最大失重速率(dw/dt) max=1.20×10 -1wt%/min、挥发分平均失重速率(dw/dt) mean=5.11×10 -2wt%/min及挥发分最大失重速率对应的温度T max=492℃、半峰宽即(dw/dt)/(dw/dt) max=1/2时的温度区间Δ 1/2=469℃。计算得到难热解材料的挥发分释放特性指数
Figure PCTCN2019076219-appb-000006
由上述三个实施例可以看出,随着升温速率的增大,铸钢件型砂的挥发分最大失重速率对应的温度T max与挥发分释放特性指数D均逐渐增大,反应了材料的热解规律。
显然,上述实施例仅仅是本发明的一部分实施例,而不是全部的实施例。上述实施例仅用于解释本发明,并不构成对本发明保护范围的限定。基于上述实施例,本领域技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,也即凡在本申请的精神和原理之内所作的所有修改、等同替换和改进等,均落在本发明要求的保护范围内。

Claims (1)

  1. 一种难热解材料的挥发分释放特性指数计算方法,其特征在于,包括下述步骤:
    步骤1:获取难热解材料在升温速率为β时每一温度下的剩余质量百分比W,形成热失重曲线W=f(T);其中,W为难热解材料的剩余质量百分比,T为温度,T=β×t,t为难热解材料的加热时间;W、T、β、t的单位分别为wt%、℃、℃/min、min;
    步骤2:对难热解材料的热失重曲线进行分析,得到每一时刻的挥发分失重速率dw/dt;其中,w为难热解材料的挥发分质量百分比,w=1-W,从而dw/dt=-β×dW/dT,w、dw/dt、dW/dT的单位分别为wt%、wt%/min、wt%/℃;
    步骤3:定义阈值
    Figure PCTCN2019076219-appb-100001
    其中,T v为难热解材料的挥发分初始析出速率,m loss为难热解材料的失重率;f的值为定值,用2wt%/min的挥发分初始析出速率与生物质能源的70%的失重率来衡量,从而f=2.86wt%/min;
    步骤4:对所述步骤1和步骤2中得到的每一温度下的剩余质量百分比数据及每一时刻的挥发分失重速率数据进行分析,确定难热解材料的失重率m loss,计算得到难热解材料的挥发分初始析出速率T v=f×m loss,从而确定当挥发分失重速率dw/dt=T v时对应的挥发分初始析出温度T s,并确定难热解材料的挥发分最大失重速率(dw/dt) max、挥发分平均失重速率(dw/dt) mean及挥发分最大失重速率对应的温度T max、半峰宽即(dw/dt)/(dw/dt) max=1/2时的温度区间Δ 1/2;其中,T s、T max、Δ 1/2的单位均为℃,(dw/dt) max、(dw/dt) mean的单位均为wt%/min;
    步骤5:计算得到难热解材料的挥发分释放特性指数
    Figure PCTCN2019076219-appb-100002
    其中,D的单位为wt% 2/min 2/℃ 3
PCT/CN2019/076219 2019-01-03 2019-02-27 难热解材料的挥发分释放特性指数计算方法 Ceased WO2020140317A1 (zh)

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CN114236088A (zh) * 2021-11-29 2022-03-25 首钢集团有限公司 焦炭残余挥发分的确定方法、确定装置和电子设备
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