本文選題：生物質(zhì)炭 + 活性有機(jī)碳��； 參考：《西北農(nóng)林科技大學(xué)》2017年博士論文

【摘要】：生物質(zhì)炭是由生物質(zhì)在完全或部分缺氧的情況下經(jīng)熱解炭化產(chǎn)生的一類多孔富碳,高度芳香化,難降解,類似活性炭的物質(zhì)。生物質(zhì)炭因原材料及制備條件的不同,其理化性質(zhì)具有較大的差異。這在一定程度上又決定了生物質(zhì)炭的環(huán)境效應(yīng)。近年來,雖然國(guó)內(nèi)外學(xué)者就不同原材料及制備條件下生物質(zhì)炭理化特性及其環(huán)境效應(yīng)開展了不少的研究,但多施用在酸性土壤中,在偏堿性的石灰性土壤中相對(duì)較少;而且關(guān)于蘋果枝條生物質(zhì)炭的制備及其性質(zhì)和應(yīng)用效果的研究更少涉及。為此,本文以蘋果枝條為原材料分別在300、400、500、600℃條件下熱解制備生物質(zhì)炭,采用掃描電鏡、紅外光譜、物理化學(xué)吸附儀等技術(shù)在研究其理化性質(zhì)、結(jié)構(gòu)差異的基礎(chǔ)上,通過室內(nèi)培養(yǎng)實(shí)驗(yàn)研究了不同溫度制備的生物質(zhì)炭在石灰性土壤(X土)中的礦化特征及其對(duì)土壤有機(jī)碳含量和組成、土壤團(tuán)聚體形成及穩(wěn)定性的影響。同時(shí),通過模擬銅鋅污染的水體和土壤,研究了生物質(zhì)炭對(duì)銅鋅的吸附特征及其對(duì)土壤中銅鋅形態(tài)轉(zhuǎn)化和生物有效性的影響。研究取得的主要結(jié)果如下:(1)熱解溫度對(duì)生物質(zhì)的理化性質(zhì)及表面結(jié)構(gòu)特征有重要影響。熱解溫度的增加,降低了生物質(zhì)炭的產(chǎn)率,揮發(fā)性組分,CEC,O,H,H/C,O/C,酸性官能團(tuán)及總官能團(tuán)的含量,而增加了其C,固定態(tài)碳,比表面積,孔隙容積及礦質(zhì)元素的含量(Cu和Mn除外)。生物質(zhì)炭pH和灰分隨著熱解溫度的增加表現(xiàn)為先增加后降低的趨勢(shì),BC500其pH值和灰分含量最高。熱穩(wěn)定分析表明,高溫制備的生物質(zhì)炭具有較高的熱穩(wěn)定性。(2)不同溫度制備的生物質(zhì)炭輸入土壤后均可顯著增加土壤有機(jī)碳含量,在300~600℃的制備溫度范圍內(nèi),以500℃制備的生物質(zhì)炭對(duì)土壤有機(jī)碳庫的提升效果最為明顯。生物質(zhì)炭輸入土壤后的礦化分解特征及其對(duì)土壤活性有機(jī)碳的影響因熱解溫度不同而有較大的差異。與對(duì)照相比,低溫(≤400℃)制備的生物質(zhì)炭在培養(yǎng)期間增加了土壤微生物量碳(MBC)、水溶性有機(jī)碳(WSOC)以及易氧化有機(jī)碳(ROC)的含量,且隨著添加比例的增加而增加,培養(yǎng)360 d后,BC300處理平均分別增加了38.25%、82.09%和63.53%;BC400處理平均分別增加了26.07%、65.61%和48.09%,且差異均達(dá)到顯著水平(P0.05);高溫(400℃)制備的生物質(zhì)炭在培養(yǎng)初期增加了土壤MBC、WSOC及ROC含量,且隨著添加比例的增加而增加,而在培養(yǎng)后期則減少了土壤MBC、WSOC、ROC含量,且隨著添加比例的增加而減少,培養(yǎng)360 d后,BC500處理平均分別減少了1.28%、13.48%和14.67%,BC600處理平均減少7.80%、14.66%和15.79%,且差異達(dá)到顯著水平(P0.05)。雙庫模型能夠很好地描述不同溫度制備的生物質(zhì)炭輸入對(duì)土壤有機(jī)碳庫及其分解速率的影響。不同溫度制備的生物質(zhì)炭輸入土壤后土壤有機(jī)碳的半衰期變化在22.77~47.83a之間,且隨著熱解溫度及生物質(zhì)炭添加比例的增加,土壤有機(jī)碳的半衰期呈現(xiàn)增加的趨勢(shì)。(3)隨著熱解溫度的升高,生物質(zhì)炭類腐殖物質(zhì)的含量呈降低的趨勢(shì),但生物質(zhì)炭類腐殖物質(zhì)的結(jié)構(gòu)趨向復(fù)雜化。生物質(zhì)炭輸入土壤后,與對(duì)照相比,低溫(≤400℃)制備的生物質(zhì)炭在培養(yǎng)期間增加了土壤胡敏酸(ha)含量,并隨著添加比例的增加而增加,培養(yǎng)360d后,bc300和bc400處理平均分別增加了69.93%和48.75%,且差異達(dá)到顯著水平(p0.05);富里酸(fa)含量在培養(yǎng)前期(240d)也有所增加,但后期則減少了土壤fa含量;高溫(400℃)制備的生物質(zhì)炭在培養(yǎng)過程中主要降低了土壤ha和fa含量(僅在培養(yǎng)初期階段引起土壤ha、fa含量的短時(shí)間增加),培養(yǎng)結(jié)束時(shí),bc500處理分別減少了34.38%和44.48%,bc600處理平均分別減少了42.84%和49.27%,且差異均達(dá)到顯著水平(p0.05)。生物質(zhì)炭輸入顯著增加了土壤胡敏素(hu)的含量,其中以bc500處理的增加效應(yīng)最大。生物質(zhì)炭輸入增加了土壤h/f比,提高了土壤hu的相對(duì)含量,增加了土壤中相對(duì)穩(wěn)定性碳的比例。高溫制備(400℃)的生物質(zhì)炭培養(yǎng)結(jié)束時(shí)顯著降低了土壤ha及fa的色調(diào)系數(shù)(Δlgk),使土壤腐殖物質(zhì)的結(jié)構(gòu)復(fù)雜化,而低溫制備的則相反。(4)生物質(zhì)炭輸入土壤均可以不同程度的增加0.5mm粒級(jí)土壤水穩(wěn)性團(tuán)聚體含量,尤其是5-8mm以及2-5mm土壤水穩(wěn)性團(tuán)聚體含量,且隨著添加比例的這種趨勢(shì)更加明顯。同時(shí),生物質(zhì)炭輸入增加了土壤團(tuán)聚體的wr0.25,mwd以及gmd,土壤團(tuán)聚體結(jié)構(gòu)穩(wěn)定性有所加強(qiáng),且隨著添加比例的增加而增加。不同制備溫度間相比,bc500對(duì)土壤水穩(wěn)性團(tuán)聚體組成及穩(wěn)定性的影響最為顯著。生物質(zhì)炭輸入均可顯著增加各粒級(jí)土壤有機(jī)碳含量,且以bc500處理下提升效果最為明顯。不同粒級(jí)間相比,生物質(zhì)炭輸入對(duì)5-8mm以及2-5mm粒級(jí)土壤水穩(wěn)性團(tuán)聚體有機(jī)碳含量的增幅最大,并隨著添加比例的增加而增加。同時(shí),生物質(zhì)炭輸入可以改變土壤有機(jī)碳在土壤水穩(wěn)性團(tuán)聚體中的分配,與對(duì)照相比,四種溫度制備的生物質(zhì)炭輸入增加了0.5mm土壤水穩(wěn)性團(tuán)聚體,尤其是5-8mm和2-5mm水穩(wěn)性團(tuán)聚體中有機(jī)碳的分配,其中bc500處理與對(duì)照相比差異均達(dá)到顯著水平。(5)不同溫度制備的蘋果枝條生物質(zhì)炭對(duì)cu(ii)和zn(ii)均具有較強(qiáng)的吸附能力。隨著生物質(zhì)炭用量的增加,生物質(zhì)炭對(duì)cu(ii)和zn(ii)吸附效率明顯降低,而去除效率顯著增加;在ph2~6范圍,隨著ph值的增加,生物質(zhì)炭對(duì)cu(ii)和zn(ii)的吸附量先增加而后降低,在ph為5.0時(shí),吸附量達(dá)到最大值;生物質(zhì)炭對(duì)cu(ii)和zn(ii)的吸附在6h內(nèi)吸附速率較快,而后吸附速率變慢,在24h內(nèi)吸附達(dá)到平衡,生物質(zhì)炭對(duì)cu(ii)和zn(ii)的吸附過程符合準(zhǔn)二級(jí)動(dòng)力學(xué)模型,表明吸附過程主要受化學(xué)吸附所控制;langmuir等溫吸附模型可以很好的描述生物質(zhì)炭對(duì)cu(ii)和zn(ii)的吸附過程,表明生物質(zhì)炭對(duì)cu(ii)和zn(ii)的吸附主要是單層吸附;生物質(zhì)炭對(duì)cu(ii)和zn(ii)的吸附量隨著溶液溫度的增加而增加,熱力學(xué)分析表明,生物質(zhì)炭對(duì)cu(ii)和zn(ii)的吸附過程是一個(gè)自發(fā)的吸熱過程。不同溫度制備的生物質(zhì)炭相比,BC500對(duì)Cu(II)和Zn(II)的吸附量在不同的條件下均為最高(除了初始pH為2.0時(shí));而不同的離子間相比,生物質(zhì)炭對(duì)Cu(II)的吸附量大于Zn(II)。(6)生物質(zhì)炭輸入可增加土壤有機(jī)結(jié)合態(tài)銅鋅的含量,減少了土壤交換態(tài)、碳酸鹽結(jié)合態(tài)以鐵錳氧化物結(jié)合態(tài)銅鋅的含量。其中,BC500處理下土壤有機(jī)結(jié)合態(tài)銅鋅的增幅最高,培養(yǎng)360 d后期土壤有機(jī)結(jié)合態(tài)銅鋅比對(duì)照平均分別增加了21.12%和39.26%。生物質(zhì)炭輸入顯著降低了土壤有效銅鋅的含量,而BC500處理導(dǎo)致土壤有效銅鋅下降的幅度最大,培養(yǎng)360 d后,土壤有效銅鋅平均比對(duì)照下降了40.58%和38.54%。有效銅鋅含量的降低導(dǎo)致其對(duì)小白菜的毒害降低,生物質(zhì)炭輸入增加了小白菜地上部分及根系干重,降低了地上部分及根系銅鋅濃度。四種溫度制備的生物質(zhì)炭相比,小白菜地上部分及根系干重表現(xiàn)為BC500BC400BC300BC600CK,而小白菜地上部分及根系銅鋅濃度則表現(xiàn)為CKBC600BC300BC400BC500。生物質(zhì)炭輸入對(duì)土壤的pH值及有機(jī)碳含量的影響是改變土壤重金屬形態(tài)分布及其有效性的重要原因。綜上所述,生物質(zhì)炭因熱解溫度不同,自身理化性質(zhì)和結(jié)構(gòu)存在較大的差異,其環(huán)境效應(yīng)也有所不同。與其他制備溫度相比,在500℃下制備的蘋果枝條生物質(zhì)炭,不僅可顯著增加土壤穩(wěn)定性有機(jī)碳的含量、土壤腐殖化程度、土壤團(tuán)聚體的穩(wěn)定和大團(tuán)聚中有機(jī)碳的分配,同時(shí),在此條件下制備的生物質(zhì)炭還可以有效吸附水體銅鋅等重金屬,且對(duì)污染土壤中銅鋅的鈍化作用最為顯著。因此,500℃是生物質(zhì)炭用于重金屬污染修復(fù)及提升偏堿性的石灰性土壤質(zhì)量的最佳制備溫度。
[Abstract]:Biomass charcoal is a kind of porous carbon rich, highly aromatic, hard to degrade and similar to activated carbon produced by pyrolysis and carbonization of biomass under the condition of complete or partial anoxia. Biomass charcoal has great differences in physical and chemical properties because of the different raw materials and preparation conditions. This determines the environment of biomass carbon to a certain extent. In recent years, many studies have been carried out on the physicochemical properties and environmental effects of biomass charcoal in different raw materials and preparation conditions, but most of them are used in acid soil and relatively less in alkaline calcareous soils; and the preparation, properties and application effects of apple branch raw carbon are also studied. In this paper, the biomass charcoal was prepared by pyrolysis of apple branches at 300400500600 degrees centigrade, using scanning electron microscope, infrared spectroscopy and physical chemical adsorption apparatus to study the physicochemical properties and structural differences of the biomass, and the biomass charcoal prepared at different temperatures was studied by indoor culture experiments. The characteristics of mineralization in gray soil (X soil) and its influence on soil organic carbon content and composition, soil aggregate formation and stability. At the same time, the adsorption characteristics of biomass carbon on copper and zinc and its influence on the transformation of copper and zinc in soil and bioavailability were studied by the simulation of copper and zinc polluted water and soil. The results are as follows: (1) the pyrolysis temperature has an important influence on the physicochemical properties and surface structure characteristics of biomass. The increase of pyrolysis temperature reduces the yield of biomass carbon, volatile components, CEC, O, H, H/C, O/C, acid functional groups and total functional groups, and increases the content of its C, fixed carbon, specific surface area, pore volume and mineral element content. (except for Cu and Mn). The biomass carbon pH and ash content increased first and then decreased with the increase of pyrolysis temperature, and the pH value and ash content of BC500 were the highest. The thermal stability analysis showed that the biomass charcoal prepared at high temperature had high thermal stability. (2) the soil organic carbon could be significantly increased after the raw material charcoal prepared at different temperatures was entered into the soil. In the range of preparation temperature at 300~600 C, biomass carbon prepared at 500 C has the most obvious effect on soil organic carbon storage. The mineralized decomposition characteristics of biomass charcoal and its influence on soil active organic carbon have great difference due to the temperature of pyrolysis. Compared with the control, low temperature (less than 400 degrees C) is prepared. The content of soil microbial biomass carbon (MBC), water soluble organic carbon (WSOC) and oxidizable organic carbon (ROC) increased during the incubation period, and increased with the increase of adding proportion. After 360 D, BC300 treatment increased by 38.25%, 82.09% and 63.53% respectively, and BC400 treatment increased by 26.07%, 65.61% and 48.09%, respectively. The high temperature (400 C) increased the content of soil MBC, WSOC and ROC in the early stage of culture, and increased with the increase of adding proportion, but decreased the content of MBC, WSOC and ROC in the later period of culture, and decreased with the increase of adding proportion, and the average of BC500 treatment decreased by 1. after the cultivation of 360 D. 28%, 13.48% and 14.67%, the average reduction of BC600 treatment was 7.80%, 14.66% and 15.79%, and the difference reached a significant level (P0.05). The dual reservoir model could well describe the effect of biomass carbon input on soil organic carbon pool and its decomposition rate. With the increase of the pyrolysis temperature and the proportion of biomass carbon, the half-life of soil organic carbon showed an increasing trend. (3) the content of biomass carbon humic substances decreased with the increase of pyrolysis temperature, but the structure of biomass carbon humic substances tended to be complex. Biomass charcoal entered the soil. (3) Compared with the control, the biomass charcoal prepared at low temperature (< 400 C) increased the soil humic acid (HA) content during the incubation period, and increased with the increase of the addition ratio. After 360D, the average increase of bc300 and bc400 was increased by 69.93% and 48.75% respectively, and the difference reached a significant level (P0.05). The content of fulvic acid (FA) was also in the early stage of culture (240d). In the later period, the soil FA content was reduced, and the biomass carbon prepared at high temperature (400 C) decreased the content of soil HA and FA in the process of culture (only in the early stage of culture, which caused the soil HA, the FA content increased in a short time). At the end of the culture, the BC500 treatment decreased by 34.38% and 44.48% respectively, and the average of bc600 treatment decreased by 42.84% respectively. And 49.27%, and the difference reached significant level (P0.05). Biomass carbon input significantly increased the content of soil humin (HU), among which the increase effect of BC500 treatment was the greatest. Biomass carbon input increased the soil h/f ratio, increased the relative content of soil Hu, increased the ratio of relative stability of soil in soil and increased the ratio of the relative stability of soil in soil. The tonal coefficient (delta LGK) of soil HA and FA was significantly reduced at the end of the material carbon culture, and the structure of soil humus was complex, while the low temperature was the opposite. (4) the content of water stable aggregates in the 0.5mm grain grade soil could be increased in different degrees, especially in 5-8mm and 2-5mm soil. In addition, with the increasing proportion of this trend, biomass carbon input increased the wr0.25, MWD and GMD of soil aggregates, and increased the stability of soil aggregates, and increased with the increase in proportion. Compared with the different preparation temperatures, the effects of BC500 on the stability of soil soil water stabilized aggregates and stability were the most. Biomass carbon input can significantly increase the content of soil organic carbon in each grain grade, and the most obvious enhancement effect under the BC500 treatment. Biomass carbon input to 5-8mm and 2-5mm grain grade soil water stable aggregate organic carbon content is the largest increase, and increase with the increase in the proportion of biomass carbon, biomass carbon, at the same time, biomass carbon. The input can change the distribution of soil organic carbon in the soil water stable aggregate. Compared with the control, the four temperature prepared biomass carbon input increased the 0.5mm soil water stable aggregate, especially the distribution of organic carbon in the 5-8mm and 2-5mm water stable aggregates, in which the difference of the BC500 treatment was significantly higher than that of the control. (5) the difference was different. The adsorption capacity of Cu (II) and Zn (II) was stronger with the temperature prepared by the biomass carbon. With the increase of biomass carbon content, the adsorption efficiency of Cu (II) and Zn (II) was obviously reduced, and the removal efficiency was significantly increased. The adsorption amount of biomass carbon to Cu (II) and II increased with the increase of pH value in the ph2~6 range. The adsorption rate reached the maximum when pH was 5. The adsorption rate of biomass carbon adsorbed on Cu (II) and Zn (II) was faster in 6h, and then the adsorption rate was slow and the adsorption reached equilibrium in 24h. The adsorption process of biomass carbon on Cu (II) and Zn (II) was in accordance with the quasi two order kinetic model, which showed that the adsorption process was mainly controlled by chemical adsorption; Langmuir was mainly controlled by chemical adsorption. The adsorption process of biomass carbon to Cu (II) and Zn (II) can be well described. It shows that the adsorption of biomass carbon to Cu (II) and Zn (II) is mainly monolayer adsorption, and the adsorption of biomass carbon to Cu (II) and Zn (II) increases with the increase of solution temperature. The adsorption of Cu (II) and Zn (II) by BC500 is the highest (except initial pH 2), while the adsorption capacity of biomass carbon to Cu (II) is greater than Zn (II). (6) biomass carbon input can increase the organic binding state of copper and zinc in soil. The content of soil exchange state is reduced, and the content of copper and zinc in the bound state of iron and manganese oxides is reduced in the carbonate bound state. Among them, the increase of copper and zinc in soil organic binding state under BC500 treatment is the highest, and the organic bound copper and zinc in the later period of 360 D is increased by 21.12% and 39.26%., respectively, and the effective copper and zinc in soil can be significantly reduced by the input of biomass carbon. BC500 treatment resulted in the largest decrease in soil effective copper and zinc. After 360 d culture, the effective copper and zinc in soil decreased by 40.58% and 38.54%. in effective copper and zinc decreased, resulting in lower toxicity of copper and zinc to Chinese cabbage. The input of biomass carbon increased the dry weight of the upper part of the Chinese cabbage and root, reduced the upper part and root of the soil. The concentration of copper and zinc. Compared with four kinds of biomass carbon, the dry weight of the upper part and root of Chinese cabbage was BC500BC400BC300BC600CK, while the concentration of copper and zinc in the upper part and root of Chinese cabbage showed that the effect of CKBC600BC300BC400BC500. biomass carbon input on the soil pH value and organic carbon content was the change of the soil heavy metal speciation. In summary, biomass charcoal has great differences in physical and chemical properties and structure because of different pyrolysis temperature, and its environmental effects are different. Compared with other preparation temperatures, the apple branch biomass carbon prepared at 500 C can not only significantly increase the content of soil stable organic carbon, but also soil decay. The degree of colonization, the stability of soil aggregates and the distribution of organic carbon in the large agglomeration, and the biomass charcoal prepared under this condition can also effectively adsorb heavy metals such as copper and zinc in water, and the passivation effect on copper and zinc in contaminated soil is the most significant. Therefore, 500 degrees centigrade is used for the remediation of heavy metal pollution and the improvement of alkaline lime by biomass carbon. The optimum preparation temperature for the quality of the soil.
【學(xué)位授予單位】：西北農(nóng)林科技大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：S141
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本文編號(hào)：2044802