Movatterモバイル変換


[0]ホーム

URL:


CN108486165A - A method of freeze/thaw improves anaerobic fermentation gas production performance with the composite modified maize straw of potassium hydroxide repeatedly - Google Patents

A method of freeze/thaw improves anaerobic fermentation gas production performance with the composite modified maize straw of potassium hydroxide repeatedly
Download PDF

Info

Publication number
CN108486165A
CN108486165ACN201810191721.3ACN201810191721ACN108486165ACN 108486165 ACN108486165 ACN 108486165ACN 201810191721 ACN201810191721 ACN 201810191721ACN 108486165 ACN108486165 ACN 108486165A
Authority
CN
China
Prior art keywords
pretreatment
freezing
thaw
freeze
potassium hydroxide
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.)
Granted
Application number
CN201810191721.3A
Other languages
Chinese (zh)
Other versions
CN108486165B (en
Inventor
李秀金
李娟�
袁海荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical TechnologyfiledCriticalBeijing University of Chemical Technology
Priority to CN201810191721.3ApriorityCriticalpatent/CN108486165B/en
Publication of CN108486165ApublicationCriticalpatent/CN108486165A/en
Application grantedgrantedCritical
Publication of CN108486165BpublicationCriticalpatent/CN108486165B/en
Activelegal-statusCriticalCurrent
Anticipated expirationlegal-statusCritical

Links

Classifications

Landscapes

Abstract

Translated fromChinese

一种反复冷冻/解冻与氢氧化钾复合改性玉米秸秆提高厌氧发酵产气性能的方法,属于可再生能源领域。本发明包含以下步骤:将玉米秸秆物料装进自封袋中,再加入不同固液比(1:5‑1:15)的自来水和不同浓度(2%‑6%)的KOH碱性试剂,然后放进‑22℃至‑41℃冷冻柜里冷冻和21℃恒温箱里解冻,其中,每冷冻12小时后拿出来解冻12小时,循环冻融2‑7天;将预处理后的物料进行中温厌氧发酵。与现有技术相比,本发明具有以下有益效果(1)预处理效果明显增强;(2)厌氧发酵周期T80明显缩短(28.1%‑40.6%);(3)沼气产量和甲烷产量明显提高(30.1%‑45.9%、40.7%‑54.9%)。The invention relates to a method for improving the gas production performance of anaerobic fermentation by compound-modifying corn stalks with repeated freezing/thawing and potassium hydroxide, belonging to the field of renewable energy. The invention comprises the following steps: putting the corn stalk material into a ziplock bag, adding tap water with different solid-liquid ratios (1:5-1:15) and KOH alkaline reagents with different concentrations (2%-6%), and then Put it in a ‑22°C to ‑41°C freezer to freeze and thaw in a 21°C incubator. Among them, after every 12 hours of freezing, take it out and thaw for 12 hours, and cycle the freeze-thaw cycle for 2‑7 days; put the pretreated material at medium temperature Anaerobic fermentation. Compared with the prior art, the present invention has the following beneficial effects (1) the pretreatment effect is significantly enhanced; (2) the anaerobic fermentation periodT80 is significantly shortened (28.1%-40.6%); (3) the biogas output and methane output are obvious increased (30.1%‑45.9%, 40.7%‑54.9%).

Description

Translated fromChinese
一种反复冷冻/解冻与氢氧化钾复合改性玉米秸秆提高厌氧发酵产气性能的方法A compound modified corn stalk with repeated freezing/thawing and potassium hydroxide improves anaerobicMethod for Fermentation Gas Production Performance

技术领域technical field

本发明属于生物质废物处理即可再生能源领域,具体涉及一种利用玉米秸秆原料进行厌氧消化以提高其产气性能的方法,尤其涉及一种通过反复冷冻/解冻与氢氧化钾复合改性玉米秸秆以提高其厌氧发酵产气性能的方法。The invention belongs to the field of biomass waste treatment and renewable energy, and specifically relates to a method for improving its gas production performance by using corn stalks for anaerobic digestion, and in particular to a compound modification by repeated freezing/thawing and potassium hydroxide A method for improving the gas production performance of corn stalks by anaerobic fermentation.

背景技术Background technique

农作物秸秆是尤为丰富且价格低廉的生物质可再生资源,我国年产农作物秸秆量达8亿多吨,其中玉米秸秆产量达2.84亿吨。因不能及时有效利用,绝大多数玉米秸秆被露天焚烧或野外堆放,严重污染大气环境,同时浪费了资源。厌氧消化技术已被证明为有效获取生物质能源的重要方法,具有低能耗、高产能等优点,目前已在我国广泛的工业化应用和规模化示范。但是玉米秸秆因其结构复杂、结晶度高,难以被微生物直接利用,进行厌氧消化时,产量低、周期长。常用的化学改性方式对木质纤维素的物理结构破坏有限,改性效果受到一定的局限,因此需要寻找一种高效的改性方式对玉米秸秆进行预处理,提高微生物对秸秆的利用率。Crop straw is a particularly abundant and cheap biomass renewable resource. The annual output of crop straw in my country reaches more than 800 million tons, of which the output of corn straw reaches 284 million tons. Most of the corn stalks are burned in open air or stacked in the field because they cannot be used effectively in a timely manner, which seriously pollutes the atmospheric environment and wastes resources. Anaerobic digestion technology has been proven to be an important method to effectively obtain biomass energy, and has the advantages of low energy consumption and high production capacity. It has been widely used in industrial applications and large-scale demonstrations in my country. However, due to its complex structure and high crystallinity, corn stalks are difficult to be directly utilized by microorganisms. When anaerobic digestion is performed, the yield is low and the cycle is long. Commonly used chemical modification methods have limited damage to the physical structure of lignocellulose, and the modification effect is limited to a certain extent. Therefore, it is necessary to find an efficient modification method to pretreat corn straw and improve the utilization rate of microorganisms on straw.

反复冷冻/解冻与氢氧化钾(KOH)复合改性玉米秸秆可以大大破坏秸秆木质纤维结构,提高产气量和生物质利用率,同时,K元素还是有机肥中的重要元素之一,厌氧消化后的沼渣沼液可以做成有机肥使用。这种复合改性方法比较适合于我国北方冬季昼夜温差大的地区。Repeated freezing/thawing combined with potassium hydroxide (KOH) to modify corn stalks can greatly destroy the lignocellulosic structure of straw, improve gas production and biomass utilization, and at the same time, K is one of the important elements in organic fertilizers. The final biogas residue and biogas slurry can be used as organic fertilizer. This composite modification method is more suitable for areas in northern my country where the temperature difference between day and night is large in winter.

冷冻/解冻可以破坏玉米秸的物理结构:通过有效的浸泡使原料充分吸水后,增加了木质纤维素的微孔结构中的含水率,其内聚力减小而容积增大,原料开始“溶胀”;在低温冷冻结冰过程中,水由原料木质纤维表面到空隙内部逐渐冷冻结冰,由于水在结冰时体积膨胀,从而在内部形成“拉伸应力”和“剪切应力”,使得木质纤维结构遭到破坏,如纤维结晶结构破坏、纤维撕裂、破裂、空隙和孔隙增大等;解冻时,靠近生物质表面的冰开始融化,而后逐渐渗入内部融化,木质纤维结构就会变得“疏松”。Freezing/thawing can destroy the physical structure of corn stalks: After the raw materials are fully absorbed by effective soaking, the water content in the microporous structure of lignocellulose is increased, the cohesive force is reduced and the volume is increased, and the raw materials begin to "swell"; In the process of low-temperature freezing and freezing, the water gradually freezes and freezes from the surface of the raw wood fiber to the interior of the void. As the volume of the water expands when it freezes, "tensile stress" and "shear stress" are formed inside, making the wood fiber The structure is destroyed, such as fiber crystal structure damage, fiber tearing, cracking, voids and pores increase, etc.; when thawing, the ice near the surface of the biomass begins to melt, and then gradually penetrates into the interior and melts, and the wood fiber structure becomes " loose".

KOH碱性试剂的添加会改变玉米秸的化学结构:经过冷冻/解冻处理后的玉米结其结构会变得疏松多孔,木质纤维孔隙更容易吸收碱溶液,皂化木质素中的醚键,水解木质素与半纤维素间的连接键,达到脱除掉半纤维素,去除掉木质素的效果,原料的微生物“可及度”和可消化性因此得到提高。同时,由于改性初始同步加入的碱试剂,解冻时可以增大溶液的渗透压和静水压,从而进一步强化木质纤维结构的疏松程度,使木质素中更多的表面羟基活性部位暴露出来,达到更有利的预处理效果。The addition of KOH alkaline reagent will change the chemical structure of corn stalks: the structure of corn stalks after freezing/thawing treatment will become loose and porous, and the pores of lignocellulosic fibers can absorb alkali solution more easily, saponify the ether bonds in lignin, and hydrolyze lignin. The link between cellulose and hemicellulose can be removed to achieve the effect of removing hemicellulose and lignin, and the microbial "accessibility" and digestibility of raw materials are thus improved. At the same time, due to the modification of the initial synchronously added alkali reagent, the osmotic pressure and hydrostatic pressure of the solution can be increased during thawing, thereby further strengthening the looseness of the lignofibrous structure and exposing more surface hydroxyl active sites in lignin. To achieve a more favorable pretreatment effect.

植物组织在冷冻过程中造成的直接损伤主要分为两种:当降温速率较慢时,细胞外溶液中首先出现冰晶,胞内外存在化学势差异,促使细胞内的水分通过细胞膜向外渗出,细胞内溶质浓度升高,导致细胞膜和胞内蛋白损伤;而当降温速率较快时,细胞内部水分来不及外渗,就会出现胞内冰晶,造成对细胞膜的机械破坏,对细胞形成致命损伤。同样的,对于生物质原料冷冻温度和降温速率对其预处理的效果也是有一定影响的。The direct damage caused by plant tissue during the freezing process is mainly divided into two types: when the cooling rate is slow, ice crystals first appear in the extracellular solution, and there is a chemical potential difference between the inside and outside of the cell, which promotes the water in the cell to leak out through the cell membrane. The increase of the concentration of solute in the cell causes damage to the cell membrane and intracellular protein; when the cooling rate is fast, the water inside the cell has no time to leak out, and intracellular ice crystals will appear, causing mechanical damage to the cell membrane and causing fatal damage to the cell. Similarly, the freezing temperature and cooling rate of biomass raw materials also have a certain impact on the pretreatment effect.

文献:黄玉龙等.小麦秸秆木质纤维素预处理技术研究(酿酒科技,2009,7:21-23.)发现:在-30℃条件下冷冻小麦秸秆24小时,检测发现处理样的还原糖含量提高,但是最大产量只达到了2.4%。文献:梁新红等.预处理方法对作物秸秆生物转化的影响(山西食品工业,2014,4:5-8)研究发现:经冷冻预处理后小麦秸秆的得糖率仅为23.03%。这些研究方法只是简单的冷冻方法,没有涉及解冻方法,且未从原料厌氧消化产气性能方面着手分析其能源化利用效果。专利CN201510013342.1介绍了一种低温水冷冻预处理玉米秸秆提高厌氧消化产气性能的方法,但是未考虑到解冻以及循环次数的影响,更是没有结合化学试剂对复合的预处理效果进行分析。文献:王新明.小麦秸秆-冻融相结合的预处理工艺研究(西安,陕西科技大学,2013),研究的是酶解率,发现纤维素酶解率为37%,且其处理效果并不是很理想。以上研究均是只考虑一种温度而未考虑到变温和复合改性对生物质原料预处理效果的影响。Literature: Huang Yulong et al. Research on Lignocellulose Pretreatment Technology of Wheat Straw (Winemaking Science and Technology, 2009, 7:21-23.) found that: after freezing wheat straw at -30°C for 24 hours, the content of reducing sugar in the treated samples was detected increased, but the maximum output only reached 2.4%. Literature: Liang Xinhong et al. The effect of pretreatment methods on the biotransformation of crop straw (Shanxi Food Industry, 2014, 4:5-8) found that the sugar yield of wheat straw after freezing pretreatment was only 23.03%. These research methods are only simple freezing methods, without involving thawing methods, and do not start to analyze the energy utilization effect of anaerobic digestion of raw materials in terms of gas production performance. Patent CN201510013342.1 introduces a method of low-temperature water freezing pretreatment of corn stalks to improve the gas production performance of anaerobic digestion, but does not consider the influence of thawing and cycle times, and does not combine chemical reagents to analyze the compound pretreatment effect . Document: Wang Xinming. Research on the pretreatment process of wheat straw-freezing and thawing (Xi'an, Shaanxi University of Science and Technology, 2013). The research is on the enzymatic hydrolysis rate. It is found that the enzymatic hydrolysis rate of cellulose is 37%, and the treatment effect is not very good ideal. The above studies only considered one temperature without considering the effect of variable temperature and compound modification on the pretreatment effect of biomass raw materials.

发明内容Contents of the invention

针对玉米秸秆原料难降解和常规预处理方法厌氧发酵产沼气低等问题,提出了本发明,以进一步提高产沼气性能。本发明的目的在于提供一种反复冷冻/解冻与氢氧化钾(KOH)复合改性玉米秸秆以提高其厌氧发酵产气性能的方法,具有操作简单、结构破坏明显及产气量高的特点。Aiming at the problems of refractory degradation of corn stalk raw materials and low biogas production by anaerobic fermentation in conventional pretreatment methods, the present invention is proposed to further improve the performance of biogas production. The purpose of the present invention is to provide a method for repeatedly freezing/thawing and potassium hydroxide (KOH) compound modified corn straw to improve its anaerobic fermentation gas production performance, which has the characteristics of simple operation, obvious structural damage and high gas production.

本发明技术方案包含如下内容:The technical solution of the present invention comprises the following contents:

(1)原料准备阶段(1) Raw material preparation stage

取玉米秸秆原料,粉碎机粉碎后干燥保存备用;Take the corn stalk raw material, pulverize it with a pulverizer, dry it and save it for later use;

(2)预处理阶段(2) Preprocessing stage

①称取玉米秸秆置于自封袋中,并将袋中空气排空;②将KOH水溶液自封袋中,揉搓均匀,其中固液质量比为1:5-1:15,KOH的质量为干玉米秸秆原料质量的2%-6%;③将混合后的自封袋置于-22℃至-41℃条件下预处理冷冻2-7天(优选4-5天),在此期间,每隔12小时拿出来常温解冻12小时之后再进行冷冻,如此循环冻融(冻融次数在2-7次,优选4-5次),每天常温解冻后待自封袋内物料温度恢复至室温,解冻时的秸秆每3小时揉搓一次,每天平均揉搓4次;在每天解冻的固定时间测定自封袋中物料的pH,当pH值不再下降时视为循环冻融预处理完成;①Weigh the corn stalks and place them in a ziplock bag, and empty the air in the bag; ②Put the KOH aqueous solution in a ziplock bag and knead evenly. 2%-6% of the raw material quality of straw; ③ place the mixed ziplock bag under the condition of -22°C to -41°C for pretreatment and freezing for 2-7 days (preferably 4-5 days), during this period, every 12 After thawing at room temperature for 12 hours, freeze and thaw again, so cycle freeze-thaw (the number of freeze-thaw times is 2-7 times, preferably 4-5 times). Knead the straw once every 3 hours, on average 4 times a day; measure the pH of the material in the ziplock bag at the fixed time of thawing every day, and when the pH value no longer drops, it is considered that the cycle freeze-thaw pretreatment is completed;

(3)厌氧消化阶段(3) Anaerobic digestion stage

将预处理所得的物料分别转移至反应器中,添加活性污泥13.6~18.5gMLSS/L,加入纯水搅拌,再通入氮气排空氧气后将其密封,最后放入恒温水箱中进行中温厌氧消化过程数十天。恒温水箱的温度为34-38℃。Transfer the pretreated materials to the reactor respectively, add 13.6-18.5gMLSS/L of activated sludge, add pure water to stir, then pass in nitrogen and exhaust oxygen, seal it, and finally put it into a constant temperature water tank for medium temperature depletion Oxygen digestion process dozens of days. The temperature of the constant temperature water tank is 34-38 ℃.

与现有技术相比,本发明具有以下有益效果:Compared with the prior art, the present invention has the following beneficial effects:

(1)改性效果明显增强。本发明的预处理时间为4天,相对于单一预处理法,物料表面结构破坏明显。(1) The modification effect is obviously enhanced. The pretreatment time of the present invention is 4 days. Compared with the single pretreatment method, the surface structure of the material is obviously destroyed.

(2)厌氧发酵周期T80明显缩短。冻融预处理条件下无酸化延滞现象,迅速进入产甲烷高峰期,明显缩短厌氧消化周期,而未预处理组则出现了明显的酸化延滞期现象。冻融预处理后的厌氧消化,T80为19-23天,比未预处理组32天缩短28.1%-40.6%,大大节约了运行成本,更适合工业生产。(2) The anaerobic fermentation cycle T80 was significantly shortened. Under freeze-thaw pretreatment conditions, there was no acidification lag phenomenon, and the peak period of methane production quickly entered, and the anaerobic digestion cycle was significantly shortened, while the acidification lag period appeared in the non-pretreatment group. For anaerobic digestion after freeze-thaw pretreatment, theT80 is 19-23 days, which is 28.1%-40.6% shorter than the 32 days of the non-pretreatment group, which greatly saves operating costs and is more suitable for industrial production.

(3)沼气产量明显提高。整个厌氧消化过程中,加入KOH试剂冷冻/解冻预处理组的厌氧消化,其单位TS产气量和单位TS产甲烷量分别比未处理组提高了30.1%-45.9%和40.7%-54.9%。因此复合法改性玉米秸秆进行厌氧消化可以大大提升其产气性能。(3) Biogas production is significantly increased. During the whole process of anaerobic digestion, the gas production per TS and the methane production per TS increased by 30.1%-45.9% and 40.7%-54.9% respectively in the anaerobic digestion of the freezing/thawing pretreatment group compared with the untreated group . Therefore, the anaerobic digestion of corn stalks modified by composite method can greatly improve its gas production performance.

附图说明Description of drawings

图1 SEM图,a、未处理;b、常温预处理;c、冷冻预处理;d、冷冻/解冻预处理Fig.1 SEM images, a, untreated; b, normal temperature pretreatment; c, freezing pretreatment; d, freezing/thawing pretreatment

图2 pH随预处理时间的变化图,a、常温预处理;b、冷冻预处理;c、冷冻/解冻预处理Figure 2 The change of pH with pretreatment time, a, normal temperature pretreatment; b, freezing pretreatment; c, freezing/thawing pretreatment

图3冷冻/解冻反复次数对玉米秸秆单位TS产气量、单位TS产甲烷量的影响Figure 3 Effects of repeated times of freezing/thawing on gas production per unit TS and methane production per unit TS of corn straw

具体实施方式Detailed ways

下面结合具体实施方式对本发明作进一步详细描述,但本发明并不限于以下实施例。The present invention will be described in further detail below in conjunction with specific embodiments, but the present invention is not limited to the following examples.

实施例中厌氧消化实验装置均由容积为1L蓝盖瓶,1L广口瓶、1L烧杯和玻璃管、乳胶管连接组成。接种物为正常运行污水处理厂厌氧消化池,加入量为18.5gMLSS/L。The anaerobic digestion experimental device in the embodiment is all made up of the volume that is 1L blue cap bottle, 1L jar, 1L beaker and glass tube, latex tube connection composition. The inoculum is the anaerobic digester of the sewage treatment plant in normal operation, and the addition amount is 18.5gMLSS/L.

实施例1Example 1

取9份重量为38.48g玉米秸秆物料(以干物质量计),用固液比(1:5、1:10和1:15的自来水)因子设计单一因子预处理实验。将上述12份原料密封在-22℃和21℃条件下冻融预处理5天,其中每隔12h后将原料拿出来常温解冻12h,解冻过程中每隔3小时揉搓1次。Taking 9 corn stalk materials with a weight of 38.48g (in terms of dry matter), a single factor pretreatment experiment was designed with solid-liquid ratio (1:5, 1:10 and 1:15 tap water) factors. The above 12 parts of raw materials were sealed at -22°C and 21°C for freeze-thaw pretreatment for 5 days, and the raw materials were taken out and thawed at room temperature for 12 hours after every 12 hours, and kneaded once every 3 hours during the thawing process.

预处理结束后加入150g正常运行污水处理厂厌氧消化池污泥(以MLSS计)作为接种物混合进行厌氧消化反应40天。同时,设置未处理组进行厌氧消化。通过排水法记录每天产沼气量,每天测定甲烷百分含量,计算甲烷总产量,然后计算T80。实验结果如下所示:After the pretreatment, 150 g of anaerobic digester sludge (calculated as MLSS) from a sewage treatment plant in normal operation was added as an inoculum and mixed for anaerobic digestion for 40 days. Meanwhile, the untreated group was set up for anaerobic digestion. Record the daily biogas production by drainage method, measure the percentage of methane every day, calculate the total methane production, and then calculate T80 . The experimental results are as follows:

表1厌氧消化产甲烷性能及出料液性质Table 1 Anaerobic digestion methane production performance and output liquid properties

上述未处理指的是将玉米秸秆物料直接接种污泥。The above-mentioned untreated means that the corn stalk material is directly inoculated with sludge.

表1所示为厌氧消化结束后单位VS产甲烷量,T80,pH,氨氮,碱度及VFA含量等厌氧消化性质分析。不同固液比预处理实验组单位VS产甲烷量为306-339mL/gTS,比未预处理组(243mL/gVS)提高26.0%-39.5%,T80为19-23天,比未预处理组(32天)缩短了28.1%-40.6%。其中,当固液比为1:10,时,厌氧消化TS产甲烷率最高(339mL/gVS),T80最短(18天),且其TS、VS去除率分别为44.3%、65.5%,明显高于未预处理组(35.8%和45.3%)。可见,冻融预处理明显缩短了厌氧消化时间,提高了负荷产甲烷率。Table 1 shows the analysis of anaerobic digestion properties such as methane production per unit VS, T80 , pH, ammonia nitrogen, alkalinity and VFA content after anaerobic digestion. The amount of methane produced per unit VS of different solid-liquid ratio pretreatment experimental groups was 306-339mL/gTS, which was 26.0%-39.5% higher than that of the unpretreated group (243mL/gVS), and theT80 was 19-23 days, which was higher than that of the unpretreated group. (32 days) shortened by 28.1%-40.6%. Among them, when the solid-liquid ratio was 1:10, the anaerobic digestion of TS had the highest methanogenic rate (339mL/gVS), the shortest T80 (18 days), and the removal rates of TS and VS were 44.3% and 65.5%, respectively, Significantly higher than the unpretreated group (35.8% and 45.3%). It can be seen that the freeze-thaw pretreatment significantly shortened the anaerobic digestion time and increased the load methane production rate.

作为评价批式厌氧消化性能及微生物新陈代谢状态的重要指标,当出料液VFA含量高于5600mg/L,pH<6.8时,系统的产甲烷过程将会受到抑制。由表1可见,本实验各组出料VFA,pH均在甲烷菌生长的适宜范围内。同时,各组氨氮和碱度也均在厌氧菌生长的最适范围(氨氮<2000mg/L、碱度>4000mg/L),能有效提高消化系统的缓冲能力,维持系统的稳定性。As an important index for evaluating the performance of batch anaerobic digestion and the metabolic state of microorganisms, when the VFA content of the effluent liquid is higher than 5600 mg/L and the pH is less than 6.8, the methane production process of the system will be inhibited. It can be seen from Table 1 that the pH of VFA discharged from each group in this experiment is within the suitable range for the growth of methanogens. At the same time, the ammonia nitrogen and alkalinity of each group are also in the optimum range for the growth of anaerobic bacteria (ammonia nitrogen <2000mg/L, alkalinity>4000mg/L), which can effectively improve the buffer capacity of the digestive system and maintain the stability of the system.

实施例2Example 2

取18份重量为38.48g玉米秸秆物料(以干物质量计),按固定固液比(1:10)加入到自封袋中混合均匀,用循环次数(2-7次)因子设计单一因子预处理实验。将上述18份原料密封在-22℃冷冻和在21℃条件下解冻进行循环冻融,每3份一组,共6组,分别循环预处理2-7天,每一组都是每隔12h后将原料拿出来常温解冻12h,解冻过程中每隔3小时揉搓1次。Take 18 parts of 38.48g corn stalk material (in terms of dry matter), add them into a ziplock bag at a fixed solid-to-liquid ratio (1:10) and mix evenly, and design a single factor pretreatment with the cycle number (2-7 times) factor experiment. The above 18 raw materials were sealed and frozen at -22°C and thawed at 21°C for cycle freezing and thawing. Each group of 3 parts, a total of 6 groups, were cycled for 2-7 days, and each group was 12 hours apart. Finally, take the raw materials out and thaw at room temperature for 12 hours, and knead once every 3 hours during the thawing process.

预处理结束后加入150g正常运行污水处理厂厌氧消化池污泥(以MLSS计)作为接种物混合进行厌氧消化反应40天。同时,设置未处理组进行厌氧消化。通过排水法记录每天产沼气量,每天测定甲烷百分含量,计算甲烷总产量,各循环次数组进行比较。实验结果如下所示:After the pretreatment, 150 g of anaerobic digester sludge (calculated as MLSS) from a sewage treatment plant in normal operation was added as an inoculum and mixed for anaerobic digestion for 40 days. Meanwhile, the untreated group was set up for anaerobic digestion. The daily biogas production is recorded by the drainage method, the percentage of methane is measured every day, the total methane production is calculated, and the groups of each cycle are compared. The experimental results are as follows:

表2厌氧消化产沼气效果Table 2 Biogas production effect of anaerobic digestion

从表2和图3可以看出,冷冻/解冻反复次数对玉米秸秆厌氧消化产气和产甲烷的影响较大。经过40天的厌氧消化反应后,可以看出随着冷冻/解冻次数的增加,玉米秸秆单位TS产气量和单位TS产甲烷量逐渐增加,在循环次数为5次时,其值达到最高,为458和275mL·gTS-1,分别比未处理提高了18.6%和21.6%,继续增加循环次数时,其产气量无明显变化,因此玉米秸秆反复冷冻/解冻改性的最佳循环次数为5次。It can be seen from Table 2 and Figure 3 that the repeated times of freezing/thawing have a great influence on the gas production and methane production of corn stover anaerobic digestion. After 40 days of anaerobic digestion, it can be seen that with the increase of freezing/thawing times, the gas production per unit TS and methane production per unit TS of corn straw gradually increased, and the values reached the highest when the number of cycles was 5 times. TS -1 were 458 and 275mL·gTS-1 , respectively increased by 18.6% and 21.6% compared with untreated. When the number of cycles continued to increase, the gas production did not change significantly. Therefore, the optimal cycle number of repeated freezing/thawing modification of corn stalks was 5 times.

实施例3Example 3

称取15份玉米秸秆物料,每份原料质量为38.48g(以干物质量计),按固定固液比(1:10)和固定KOH试剂质量百分含量(0%、6%)加入到自封袋中混合均匀,置于-22℃和21℃以及-41℃和21℃条件下冻融预处理5天,同时设置添加10倍自来水组、冷冻组、常温(21℃)处理组和未预处理组。Weigh 15 parts of corn stalk materials, each raw material has a mass of 38.48g (in terms of dry matter), and add it to the self-sealing Mix well in the bag, and place it at -22°C and 21°C and -41°C and 21°C for freeze-thaw pretreatment for 5 days. treatment group.

预处理结束后加入150g正常运行污水处理厂厌氧消化池污泥(以MLSS计)作为接种物混合进行厌氧消化反应40天。同时,设置未处理组进行厌氧消化。通过排水法记录每天产沼气量,每天测定甲烷百分含量,计算甲烷总产量,各预处理组进行比较。实验结果如下所示:After the pretreatment, 150 g of anaerobic digester sludge (calculated as MLSS) from a sewage treatment plant in normal operation was added as an inoculum and mixed for anaerobic digestion for 40 days. Meanwhile, the untreated group was set up for anaerobic digestion. The daily biogas production was recorded by the drainage method, the percentage of methane was measured every day, the total methane production was calculated, and each pretreatment group was compared. The experimental results are as follows:

表3厌氧消化产沼气效果Table 3 Biogas production effect of anaerobic digestion

上述温度21和-22分别指在21℃和-22℃稳定保持4天,-22+21指在-22℃冻融在21℃解冻循环4天,-41+21指在-41℃冻融在21℃解冻循环4天。The above temperature 21 and -22 refer to stable storage at 21°C and -22°C for 4 days respectively, -22+21 refers to freeze-thaw at -22°C and thaw cycle at 21°C for 4 days, -41+21 refers to freeze-thaw at -41°C Thaw cycle at 21 °C for 4 days.

从表3可以看出,经过40天的厌氧消化反应,只添加10倍水的冻融组(0%)其物料厌氧消化单位TS产气量、单位TS产甲烷量均比冷冻(-22℃)预处理组、常温(21℃)预处理组和未处理组物料厌氧消化单位TS产气量、单位TS产甲烷量高,而添加了KOH试剂的冻融组(-22+21℃)其物料厌氧发酵甲烷产量相比于只添加10倍水的冻融组(0%)有显著提高。另外,在两组冻融预处理组(-22+21℃和-41+21℃)中,当冷冻温度为-22℃时,玉米秸秆厌氧消化产气性能较优。As can be seen from Table 3, through the anaerobic digestion reaction of 40 days, only add 10 times of water freeze-thaw group (0%) its material anaerobic digestion unit TS gas production, unit TS methane production are all higher than freezing (-22 ℃) Pretreatment group, normal temperature (21℃) pretreatment group and untreated group have high gas production per unit TS and methane production per unit TS in anaerobic digestion, while the freeze-thaw group with KOH reagent added (-22+21℃) Compared with the freeze-thaw group (0%) that only added 10 times of water, the methane output of its material anaerobic fermentation was significantly improved. In addition, in the two freeze-thaw pretreatment groups (-22+21°C and -41+21°C), when the freezing temperature was -22°C, the performance of anaerobic digestion of corn straw was better.

在整个厌氧消化组中,加入KOH试剂冷冻/解冻预处理组的厌氧消化,其单位TS产气量和单位TS产甲烷量分别比未处理组提高了30.1%-45.9%和40.7%-54.9%,其提高量远高于黄玉龙小麦秸秆木质纤维素预处理技术研究中小麦酶解的还原糖含量(2.4%)和梁新红预处理方法对作物秸秆生物转化的影响研究中小麦秸秆的得糖率(23.03%),以及王新明小麦秸秆-冻融相结合的预处理工艺研究中小麦的酶解率(37%)。因此本文中的复合法改性玉米秸秆进行厌氧消化可以大大提升其产气性能。In the whole anaerobic digestion group, the gas production per unit TS and the methane production per unit TS increased by 30.1%-45.9% and 40.7%-54.9% respectively in the anaerobic digestion group added KOH reagent freezing/thawing pretreatment group compared with the untreated group %, which is much higher than the reducing sugar content (2.4%) of enzymatic hydrolysis of wheat in Huang Yulong's research on wheat straw lignocellulose pretreatment technology and the sugar yield of wheat straw in Liang Xinhong's research on the impact of pretreatment methods on crop straw biotransformation rate (23.03%), and the enzymatic hydrolysis rate (37%) of wheat in Wang Xinming's wheat straw-freeze-thaw combination pretreatment process research. Therefore, the anaerobic digestion of corn straw modified by the composite method in this paper can greatly improve its gas production performance.

Claims (3)

1. weighing maize straw to be placed in valve bag, and air in bag is emptied;2. by KOH aqueous solution valve bags, rubbing is equalEven, wherein solid-liquid mass ratio is 1:5-1:15, KOH quality is the 2%-6% of Dry corn stalk stalk material quality;3. after mixingValve bag be placed in -22 DEG C to -41 DEG C under the conditions of pretreatment freezing 2-7 days, during this period, room temperature solution was taken out every 12 hoursIt is freezed again after freezing 12 hours, such circulating freezing resistance, waits for that temperature of charge restores to room in valve bag after daily normal temperature unfreezingTemperature, the stalk rubbing in every 3 hours when defrosting is primary, averagely rubs 4 times daily;Valve bag is measured in the set time thawed dailyThe pH of middle material is considered as circulating freezing resistance pretreatment when pH value no longer declines and completes;
CN201810191721.3A2018-03-082018-03-08Method for improving anaerobic fermentation gas production performance by repeatedly freezing/thawing and potassium hydroxide composite modified corn strawActiveCN108486165B (en)

Priority Applications (1)

Application NumberPriority DateFiling DateTitle
CN201810191721.3ACN108486165B (en)2018-03-082018-03-08Method for improving anaerobic fermentation gas production performance by repeatedly freezing/thawing and potassium hydroxide composite modified corn straw

Applications Claiming Priority (1)

Application NumberPriority DateFiling DateTitle
CN201810191721.3ACN108486165B (en)2018-03-082018-03-08Method for improving anaerobic fermentation gas production performance by repeatedly freezing/thawing and potassium hydroxide composite modified corn straw

Publications (2)

Publication NumberPublication Date
CN108486165Atrue CN108486165A (en)2018-09-04
CN108486165B CN108486165B (en)2022-03-25

Family

ID=63338231

Family Applications (1)

Application NumberTitlePriority DateFiling Date
CN201810191721.3AActiveCN108486165B (en)2018-03-082018-03-08Method for improving anaerobic fermentation gas production performance by repeatedly freezing/thawing and potassium hydroxide composite modified corn straw

Country Status (1)

CountryLink
CN (1)CN108486165B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication numberPriority datePublication dateAssigneeTitle
CN109486864A (en)*2018-11-142019-03-19江南大学A kind of solid-state alkali treatment method improving organic waste anaerobic fermentation efficiency
CN111926046A (en)*2020-08-312020-11-13西北农林科技大学Method for improving performance of wheat straw anaerobic fermentation biogas production by low-temperature freeze thawing pretreatment
CN112301062A (en)*2020-11-262021-02-02戴加兵 A kind of method for producing methane by anaerobic fermentation of corn stover
CN113621655A (en)*2021-05-182021-11-09黑龙江省农业科学院农村能源与环保研究所Method for improving biogas yield of straw anaerobic fermentation by using straw freeze-thaw cycle pretreatment
CN115287305A (en)*2022-05-302022-11-04中国科学院过程工程研究所 A freeze-thaw cycle coupled pretreatment method for green disassembly of lignocellulose and its application
CN117204514A (en)*2023-09-142023-12-12禹城保立康生物饲料有限公司 A method for making leaf-eating grass fermented liquid feed that improves lactation performance of sows

Citations (1)

* Cited by examiner, † Cited by third party
Publication numberPriority datePublication dateAssigneeTitle
CN104593429A (en)*2015-01-112015-05-06北京化工大学Method for low-temperature pretreatment of corn straw to improve gas production performance of anaerobic digestion by combination of sodium hydroxide and ammonia water

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication numberPriority datePublication dateAssigneeTitle
CN104593429A (en)*2015-01-112015-05-06北京化工大学Method for low-temperature pretreatment of corn straw to improve gas production performance of anaerobic digestion by combination of sodium hydroxide and ammonia water

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
杰夫(MUHAMMAD JAFFAR)(穆罕默德•贾法尔): "KOH预处理强化小麦秸秆厌氧消化的生物甲烷生产和肥料价值", 《中国博士学位论文全文数据库》*
王新明: "小麦秸秆冻融—酸碱相结合的预处理工艺研究", 《中国硕士学位论文全文数据库》*

Cited By (6)

* Cited by examiner, † Cited by third party
Publication numberPriority datePublication dateAssigneeTitle
CN109486864A (en)*2018-11-142019-03-19江南大学A kind of solid-state alkali treatment method improving organic waste anaerobic fermentation efficiency
CN111926046A (en)*2020-08-312020-11-13西北农林科技大学Method for improving performance of wheat straw anaerobic fermentation biogas production by low-temperature freeze thawing pretreatment
CN112301062A (en)*2020-11-262021-02-02戴加兵 A kind of method for producing methane by anaerobic fermentation of corn stover
CN113621655A (en)*2021-05-182021-11-09黑龙江省农业科学院农村能源与环保研究所Method for improving biogas yield of straw anaerobic fermentation by using straw freeze-thaw cycle pretreatment
CN115287305A (en)*2022-05-302022-11-04中国科学院过程工程研究所 A freeze-thaw cycle coupled pretreatment method for green disassembly of lignocellulose and its application
CN117204514A (en)*2023-09-142023-12-12禹城保立康生物饲料有限公司 A method for making leaf-eating grass fermented liquid feed that improves lactation performance of sows

Also Published As

Publication numberPublication date
CN108486165B (en)2022-03-25

Similar Documents

PublicationPublication DateTitle
CN108486165A (en)A method of freeze/thaw improves anaerobic fermentation gas production performance with the composite modified maize straw of potassium hydroxide repeatedly
CN105420282B (en) A method for improving the gas production performance of mixed anaerobic digestion of straw and manure by biochemical pretreatment of corn straw
Lunprom et al.Bio-hythane production from residual biomass of Chlorella sp. biomass through a two-stage anaerobic digestion
AU2020100873A4 (en)The Method For Improving The Biogas Production Performance Of Wet Anaerobic Digestion Of Straw By Micro Comminution Pretreatment
Yuan et al.Effect on anaerobic digestion performance of corn stover by freezing–thawing with ammonia pretreatment
CN108384813A (en)A kind of method of calcium oxide and biogas slurry combined pretreatment raising rice straw anaerobic digestion gas production performance
CN105755052A (en)Town multi-element organic waste for preparing biogas and method for preparing biogas from same
CN102747107A (en)Methane fermenting method
CN1888073B (en) Biogas fermentation method of straw pretreated by compound bacterial agent
CN110055172A (en)A kind of agricultural wastes dry anaerobic fermentation self-con-tained unit and autocontrol operation method
CN104399735B (en)A kind of preprocess method of stalk biomass
CN101775412A (en)Method for preparing biogas by using lignocellulose
CN107988269A (en)A kind of Cold pretreatment of lignocellulose biomass and its method for preparing hydrogen
CN106480101B (en) The method of N, P, K compound nutrient pretreatment to improve the gas production performance of anaerobic digestion of corn straw
CN102154374A (en)Method for preparing marsh gas by pretreating rice straws with acid
CN106119289A (en)A kind of composite flora Synergistic degradation stalk cellulose and the combined pretreatment method of fermentation and hydrogen production
SittijundaBiogas production from hydrolysate napier grass by co-digestion with slaughterhouse wastewater using anaerobic mixed cultures
CN101445810B (en)Method for preparing hydrogen by fermenting biologically pretreated straw
CN111676250A (en) A kind of method for ferric chloride pretreatment to strengthen lignocellulose anaerobic fermentation for methane production
CN102020404A (en)Method for improving fermentation capability of slurry dry process
CN114181977A (en) A kind of pretreatment method and application of enhancing methane-producing performance of straw with anaerobic fermentation self-product
CN101914576B (en)Method for producing ethanol and methane by mixed fermentation of paper-making sludge and monosodium glutamate waste liquid
CN104593429B (en) Method for improving gas production performance of anaerobic digestion by combining sodium hydroxide and ammonia water with low temperature pretreatment of corn stover
CN101368190A (en) Sodium hydroxide wet solid-state normal temperature treatment method to improve the biogas production of corn stalks
CN104593431B (en)The method that water at low temperature freezing pretreatment maize straw improves anaerobic digestion gas production performance

Legal Events

DateCodeTitleDescription
PB01Publication
PB01Publication
SE01Entry into force of request for substantive examination
SE01Entry into force of request for substantive examination
GR01Patent grant
GR01Patent grant

[8]ページ先頭

©2009-2025 Movatter.jp