鎳基、鈷基添加劑對高硫焦煤熱解過程中硫遷移行為的影響
發(fā)布時(shí)間：2018-08-01 08:59
【摘要】：隨著煤炭資源的大幅度開采利用,優(yōu)質(zhì)煉焦煤資源日益短缺,高硫煤等非優(yōu)質(zhì)煤資源儲量相對較大,但硫含量高的特點(diǎn)在一定程度上限制了其利用。為了緩解當(dāng)前優(yōu)質(zhì)煉焦煤資源緊缺的問題,在保證焦炭質(zhì)量的前提下,利用現(xiàn)有的高硫煉焦煤資源,合理調(diào)控高硫煤在煉焦過程中硫分的分布行為,有效降低焦中硫的比例,既能擴(kuò)大煉焦用煤種類,又能有效降低焦炭生產(chǎn)成本。煤中硫主要分為無機(jī)硫和有機(jī)硫,無機(jī)硫可以通過浮選等傳統(tǒng)物理方法脫除,而有機(jī)硫比較難脫除。基于此,本文選取一種富含有機(jī)硫的高硫焦煤,期望通過加壓浸漬的負(fù)載方法向煤中引入鎳基添加劑和鈷基添加劑,以達(dá)到合理調(diào)控煤中有機(jī)硫的熱變遷。在固定床上進(jìn)行原煤及負(fù)載添加劑煤樣的程序升溫?zé)峤鈱?shí)驗(yàn),重點(diǎn)考察無機(jī)添加劑對煤中硫遷移轉(zhuǎn)化過程的影響,得到的主要結(jié)果表現(xiàn)在以下幾個(gè)方面:(1)鎳基添加劑對高硫煤熱解過程中硫變遷行為的影響:鎳基添加劑對煤熱解過程中硫變遷行為的作用受負(fù)載壓力和金屬鹽濃度的共同影響。當(dāng)金屬鹽濃度為0.1%時(shí),鎳對煤樣0.1-0.5-Ni(鎳基金屬鹽濃度為0.1%,負(fù)載壓力為0.5 MPa制得的煤樣)熱解時(shí)含硫氣體的釋放有抑制作用,對其他負(fù)載煤樣則表現(xiàn)為促進(jìn)作用;當(dāng)金屬鹽濃度較高時(shí),鎳對煤熱解過程中含硫氣體釋放有促進(jìn)作用;但是當(dāng)負(fù)載壓力為1MPa時(shí),鎳在煤熱解過程中有一定的固硫作用,致使焦中硫含量增加。當(dāng)負(fù)載壓力一定,金屬鹽濃度不同,鎳對煤熱解過程中硫在氣、固相分配的影響不同。當(dāng)負(fù)載壓力為0.1 MPa時(shí),鎳對煤樣熱解過程中含硫氣體的釋放只有促進(jìn)作用,而與金屬鹽濃度大小無關(guān),此時(shí)焦中硫含量均降低;當(dāng)負(fù)載壓力為0.5 MPa,金屬鹽濃度低時(shí),鎳對煤熱解過程中含硫氣體的釋放表現(xiàn)出抑制作用,而金屬鹽濃度較高時(shí),則表現(xiàn)出促進(jìn)作用;負(fù)載壓力為1 MPa時(shí),鎳對煤熱解過程中含硫氣體的釋放只表現(xiàn)為促進(jìn)作用,且隨著金屬鹽濃度的增大,促進(jìn)作用先增強(qiáng)后減弱。(2)鈷基添加劑對高硫煤熱解過程中硫變遷行為的影響:鈷基添加劑對煤熱解過程中硫變遷行為的作用與鎳基額添加劑一樣,同樣受負(fù)載壓力和金屬鹽濃度的共同影響。鈷對煤熱解過程中含硫氣體釋放表現(xiàn)為促進(jìn)作用,與負(fù)載壓力無關(guān)。當(dāng)金屬鹽濃度為0.1%時(shí),隨著負(fù)載壓力的升高,配鈷基添加劑煤樣熱解過程中含硫氣體的釋放量先增加后減少,焦中硫含量則先降低后增加。而金屬鹽濃度為2%時(shí),焦中硫含量均降低,但降低程度不同。負(fù)載壓力一定,金屬鹽濃度不同時(shí),除1-1-Co煤樣外,其他所有煤樣熱解焦中的硫含量均不同程度降低。當(dāng)負(fù)載壓力為1 MPa,金屬鹽濃度為1%時(shí),煤熱解過程中含硫氣體的釋放量有所減少,且焦中硫含量也最低,說明該煤樣熱解過程中有更多硫遷移至焦油中。(3)兩種無機(jī)添加劑對煤熱解焦中硫含量影響的差異性分析。低金屬鹽濃度和高金屬鹽濃度下,兩種添加劑對煤熱解焦中硫含量的影響完全相反。當(dāng)金屬鹽濃度為0.1%時(shí),隨著負(fù)載壓力的升高,負(fù)載Ni基和Co基添加劑的煤焦中硫含量都呈現(xiàn)出先降低后升高的趨勢,但Co添加劑比Ni添加劑的作用更顯著。當(dāng)金屬鹽濃度為2%時(shí),雖然Ni基添加劑和Co基添加劑的煤焦中硫含量隨著負(fù)載壓力的升高,也表現(xiàn)出同增同減的趨勢,但是Co添加劑降低煤焦中硫含量的效果卻比Ni添加劑差。
[Abstract]:With the large mining and utilization of coal resources, high quality coking coal resources are scarce and the reserves of high sulfur coal and other non quality coal resources are relatively large, but the high sulfur content has limited its utilization to a certain extent. In order to alleviate the shortage of high quality coking coal resources at present, the existing high sulfur content is used to ensure the quality of coke, and the existing high sulfur is used. Coking coal resources can be used to rationally regulate the distribution of sulfur in coking process, effectively reduce the proportion of sulfur in coke, which can not only expand the type of coking coal, but also effectively reduce the cost of coke production. The sulfur in coal is mainly divided into inorganic and organic sulfur, and the inorganic sulfur can be removed by the traditional physical methods, such as flotation, and the organic sulfur is difficult to remove. In addition, based on this, this paper selects a high sulfur coking coal rich in organic sulfur, and expects to introduce nickel based additives and cobalt based additives into coal by pressure impregnation method, so as to achieve the reasonable regulation of the thermal change of organic sulfur in coal. The effects of additives on the sulfur migration and transformation in coal are mainly shown in the following aspects: (1) the effect of nickel based additives on the sulfur change behavior during the pyrolysis of high sulfur coal: the effect of nickel based additives on the sulfur change behavior in the process of coal pyrolysis is affected by the load pressure and the concentration of metal salt. When the concentration of metal salt is 0 At.1%, nickel has an inhibitory effect on the release of sulfur containing gas when the coal sample 0.1-0.5-Ni (the concentration of nickel base metal salt is 0.1%, and the load pressure is 0.5 MPa), and is promoted to other loaded coal samples. When the concentration of metal salt is high, nickel can promote the release of sulfur containing gas in the coal pyrolysis process; but when the load pressure is at the load pressure, In the process of 1MPa, nickel has a certain sulfur fixation process in the process of coal pyrolysis, resulting in an increase in sulfur content in the coke. When the load pressure is certain, the concentration of metal salt is different, the influence of nickel on gas and solid phase distribution is different in the process of coal pyrolysis. When the load pressure is 0.1 MPa, the nickel can only promote the release of sulfur containing gas in the coal sample pyrolysis process, but with the metal. The concentration of salt is irrelevant, and the sulfur content in the coke is reduced at this time. When the load pressure is 0.5 MPa and the concentration of metal salt is low, nickel inhibits the release of sulfur gas in the coal pyrolysis process, while the metal salt concentration is higher, while the load pressure is 1 MPa, the release of sulphur containing gas in the coal pyrolysis process is only shown. In order to promote the effect, and with the increase of metal salt concentration, the promotion effect first strengthened and then weakened. (2) the effect of cobalt base additive on the sulfur change behavior during the pyrolysis of high sulfur coal: the effect of cobalt base additive on the sulfur change behavior in the process of coal pyrolysis is the same as the nickel base additive, the same effect of the load pressure and the concentration of metal salt. The release of sulfur containing gas in the process of coal pyrolysis is not related to the load pressure. When the metal salt concentration is 0.1%, with the increase of the load pressure, the release amount of sulfur containing gas is increased first and then decreased with the increase of the load pressure. The sulfur content in the coke is reduced first and then increases. While the concentration of metal salt is 2%, the sulfur content in the coke is contained. When the load pressure is different, the load pressure is certain, the concentration of metal salt is not at the same time. Except 1-1-Co coal sample, the sulfur content in all kinds of coal sample pyrolysis coke is reduced in varying degrees. When the load pressure is 1 MPa and the concentration of metal salt is 1%, the release amount of sulfur containing gas is reduced in the process of coal pyrolysis, and the sulfur content in the coke is also the lowest. In the process of coal pyrolysis, more sulfur is migrated to tar. (3) the difference analysis of the influence of two inorganic additives on the Jiao Zhongliu content of coal pyrolysis. Under the concentration of low metal salt and the concentration of high metal salt, the effect of the two additives on the sulfur content in coal pyrolysis coke is completely opposite. When the concentration of metal salt is 0.1%, it is negative with the increase of load pressure. The sulfur content in coal char with Ni and Co based additives shows a tendency to decrease first and then increase, but the effect of Co additive is more significant than that of Ni additive. When the concentration of metal salt is 2%, the sulfur content in char with Ni base additive and Co based additive increases with the increase of load pressure, but it also shows the same increase and decrease, but Co additive. The effect of reducing sulfur content in coal char is worse than that of Ni additive.
【學(xué)位授予單位】：太原理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ530.2
本文編號：2157061
[Abstract]:With the large mining and utilization of coal resources, high quality coking coal resources are scarce and the reserves of high sulfur coal and other non quality coal resources are relatively large, but the high sulfur content has limited its utilization to a certain extent. In order to alleviate the shortage of high quality coking coal resources at present, the existing high sulfur content is used to ensure the quality of coke, and the existing high sulfur is used. Coking coal resources can be used to rationally regulate the distribution of sulfur in coking process, effectively reduce the proportion of sulfur in coke, which can not only expand the type of coking coal, but also effectively reduce the cost of coke production. The sulfur in coal is mainly divided into inorganic and organic sulfur, and the inorganic sulfur can be removed by the traditional physical methods, such as flotation, and the organic sulfur is difficult to remove. In addition, based on this, this paper selects a high sulfur coking coal rich in organic sulfur, and expects to introduce nickel based additives and cobalt based additives into coal by pressure impregnation method, so as to achieve the reasonable regulation of the thermal change of organic sulfur in coal. The effects of additives on the sulfur migration and transformation in coal are mainly shown in the following aspects: (1) the effect of nickel based additives on the sulfur change behavior during the pyrolysis of high sulfur coal: the effect of nickel based additives on the sulfur change behavior in the process of coal pyrolysis is affected by the load pressure and the concentration of metal salt. When the concentration of metal salt is 0 At.1%, nickel has an inhibitory effect on the release of sulfur containing gas when the coal sample 0.1-0.5-Ni (the concentration of nickel base metal salt is 0.1%, and the load pressure is 0.5 MPa), and is promoted to other loaded coal samples. When the concentration of metal salt is high, nickel can promote the release of sulfur containing gas in the coal pyrolysis process; but when the load pressure is at the load pressure, In the process of 1MPa, nickel has a certain sulfur fixation process in the process of coal pyrolysis, resulting in an increase in sulfur content in the coke. When the load pressure is certain, the concentration of metal salt is different, the influence of nickel on gas and solid phase distribution is different in the process of coal pyrolysis. When the load pressure is 0.1 MPa, the nickel can only promote the release of sulfur containing gas in the coal sample pyrolysis process, but with the metal. The concentration of salt is irrelevant, and the sulfur content in the coke is reduced at this time. When the load pressure is 0.5 MPa and the concentration of metal salt is low, nickel inhibits the release of sulfur gas in the coal pyrolysis process, while the metal salt concentration is higher, while the load pressure is 1 MPa, the release of sulphur containing gas in the coal pyrolysis process is only shown. In order to promote the effect, and with the increase of metal salt concentration, the promotion effect first strengthened and then weakened. (2) the effect of cobalt base additive on the sulfur change behavior during the pyrolysis of high sulfur coal: the effect of cobalt base additive on the sulfur change behavior in the process of coal pyrolysis is the same as the nickel base additive, the same effect of the load pressure and the concentration of metal salt. The release of sulfur containing gas in the process of coal pyrolysis is not related to the load pressure. When the metal salt concentration is 0.1%, with the increase of the load pressure, the release amount of sulfur containing gas is increased first and then decreased with the increase of the load pressure. The sulfur content in the coke is reduced first and then increases. While the concentration of metal salt is 2%, the sulfur content in the coke is contained. When the load pressure is different, the load pressure is certain, the concentration of metal salt is not at the same time. Except 1-1-Co coal sample, the sulfur content in all kinds of coal sample pyrolysis coke is reduced in varying degrees. When the load pressure is 1 MPa and the concentration of metal salt is 1%, the release amount of sulfur containing gas is reduced in the process of coal pyrolysis, and the sulfur content in the coke is also the lowest. In the process of coal pyrolysis, more sulfur is migrated to tar. (3) the difference analysis of the influence of two inorganic additives on the Jiao Zhongliu content of coal pyrolysis. Under the concentration of low metal salt and the concentration of high metal salt, the effect of the two additives on the sulfur content in coal pyrolysis coke is completely opposite. When the concentration of metal salt is 0.1%, it is negative with the increase of load pressure. The sulfur content in coal char with Ni and Co based additives shows a tendency to decrease first and then increase, but the effect of Co additive is more significant than that of Ni additive. When the concentration of metal salt is 2%, the sulfur content in char with Ni base additive and Co based additive increases with the increase of load pressure, but it also shows the same increase and decrease, but Co additive. The effect of reducing sulfur content in coal char is worse than that of Ni additive.
【學(xué)位授予單位】：太原理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ530.2
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