本文關(guān)鍵詞： 小麥廢水 膜分離 戊聚糖 纖維素柱柱層析 分離方法　出處：《華南理工大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：小麥加工的廢水中含有大量可回收、利用價(jià)值高的戊聚糖、蛋白質(zhì)等有機(jī)物,但當(dāng)前小麥淀粉加工廠很少會(huì)對(duì)其重視,大部分都是排放到污水處理站處理,有的甚至直接排放。這不僅造成資源的浪費(fèi),還會(huì)對(duì)環(huán)境造成嚴(yán)重污染。傳統(tǒng)的廢水處理方法如蒸發(fā)濃縮、生物處理、化學(xué)處理等耗能大、流程長(zhǎng)、處理成本高,對(duì)企業(yè)造成較為沉重的經(jīng)濟(jì)負(fù)擔(dān)。小麥廢水的低成本處理和資源的高價(jià)值回收利用是全行業(yè)的共性難題。本文提出利用直接膜分離法、層析交換分離法、沉淀蛋白/膜分離組合法、酶解蛋白/膜分離組合法等四種途徑從小麥淀粉廢水中分離回收高價(jià)值的戊聚糖,分別展開(kāi)試驗(yàn)研究。根據(jù)實(shí)驗(yàn)結(jié)果對(duì)四種方法做出橫向比選,為小麥淀粉廢水中戊聚糖的回收利用工程化提供參考依據(jù)。此外,本文還對(duì)戊聚糖的單糖組成進(jìn)行了光譜辨識(shí),檢測(cè)了聚合物的分支程度。直接膜分離法實(shí)驗(yàn)研究表明,當(dāng)透過(guò)液為100m L,截留液700m L時(shí),10000Dalton(以下簡(jiǎn)稱Da)超濾膜對(duì)戊聚糖的截留率達(dá)到97.81%,對(duì)蛋白質(zhì)的截留率達(dá)到97.75%,這兩種物質(zhì)的截留液和透過(guò)液的濃度比值分別為15.29和10.48,表明10000Da的超濾膜對(duì)這兩種物質(zhì)有很好的截留能力。而還原糖和氨基酸的截留液和透過(guò)液濃度比值都接近1,表明10000Da超濾膜對(duì)還原糖和氨基酸沒(méi)有截留能力。實(shí)驗(yàn)用20000Da和50000Da膜片進(jìn)行超濾實(shí)驗(yàn),數(shù)據(jù)顯示蛋白質(zhì)和戊聚糖的截留液和透過(guò)液濃度比值都接近1,表明這兩種膜片對(duì)蛋白質(zhì)和戊聚糖都沒(méi)有截留功能。本實(shí)驗(yàn)分別用蛋白酶酶解、熱凝聚法、生物絮凝劑、等電點(diǎn)沉淀法、三氯乙酸絮凝法,五種方法預(yù)先去除小麥淀粉加工廢水中的蛋白質(zhì),為膜分離回收戊聚糖提供前提條件。實(shí)驗(yàn)結(jié)果顯示,蛋白質(zhì)的去除效果有很大差異。蛋白質(zhì)去除率分別是蛋白酶法(87.11%)三氯乙酸法(68.50%)天然高分子絮凝法(20.29%)熱凝聚法(17.51%)等電點(diǎn)法(8.56%)。同時(shí),五種處理方法戊聚糖的損失率分別為:三氯乙酸法(22.89%)蛋白酶法(12.93%)有機(jī)高分子絮凝法(11.21%)熱凝聚法(9.16%)等電點(diǎn)法(8.24%)。以蛋白質(zhì)去除率和戊聚糖保留率為考核指標(biāo),最終確定蛋白酶解方法為適宜的去蛋白方法。廢水經(jīng)蛋白酶預(yù)處理后蛋白去除率為87.11%,戊聚糖只損失12.93%。后續(xù)再采用直接膜分離法,使用10000Da的膜,戊聚糖基本上能夠被截留回收。在上述實(shí)驗(yàn)的基礎(chǔ)上,本實(shí)驗(yàn)設(shè)計(jì)了酶解和膜分離組合的方法:先將蛋白質(zhì)分解為氨基酸,然后再用10000Da超濾膜將氨基酸、還原糖和戊聚糖分開(kāi)。酶解/超濾實(shí)驗(yàn)結(jié)果表明,當(dāng)透過(guò)液達(dá)到待分離液體積的1.5倍時(shí)(循環(huán)過(guò)程補(bǔ)水),全過(guò)程蛋白質(zhì)總的去除率為92.27%,對(duì)還原糖和氨基酸(蛋白質(zhì)酶解產(chǎn)物)的保留率僅24.16%和28.10%,戊聚糖總的保留率為77.36%。10000Da的超濾膜對(duì)還原糖和蛋白質(zhì)降解后的產(chǎn)物氨基酸無(wú)截留功能。因此,增加循環(huán)次數(shù)、延長(zhǎng)超濾時(shí)間能達(dá)到去除廢水中蛋白質(zhì)水解產(chǎn)物(氨基酸)和還原糖、截留戊聚糖的效果。本文嘗試了層析交換分離法回收戊聚糖。采用DEAE-52纖維素作為層析介質(zhì),以水為洗脫劑,加入適量Na Cl增強(qiáng)洗脫效果。分段收集洗脫液,用凍融分析法定性判斷分離效果,采用紫外分光光度法分析蛋白質(zhì)含量,選擇離子色譜定量分析戊聚糖(包含還原糖)。同時(shí),用紅外光譜輔助分析判斷洗脫液中固體成分的化學(xué)物質(zhì)結(jié)構(gòu)。實(shí)驗(yàn)結(jié)果表明,整個(gè)戊聚糖洗脫分布曲線完全符合典型的層析分離規(guī)律,分離操作條件選擇是成功的,DEAE-52纖維素樹(shù)脂適合分離戊聚糖,分離效果良好。凍融法和紫外分光光度法檢測(cè)結(jié)果證明了層析洗脫液中絕大部分是可溶性戊聚糖,基本不含蛋白質(zhì)和氨基酸等雜質(zhì)。紅外光譜圖中917.12 cm—1處顯現(xiàn)β—D—半乳吡喃糖的特征峰,841.12 cm—1處出現(xiàn)α—D—葡萄吡喃糖的特征峰,表明該多糖有α-糖苷鍵和β-糖苷鍵。將回收得到的戊聚糖采用酸水解法轉(zhuǎn)化為單糖,用糖離子色譜儀檢測(cè)單糖種類歸屬。檢測(cè)結(jié)果表明小麥淀粉廢水中分離出來(lái)的戊聚糖主要由阿拉伯糖、木糖、半乳糖和葡萄糖四種單糖組成。N(Ara)/n(Xyl)比值為0.92,反映出戊聚糖聚合物的分支程度比較大�？傮w評(píng)價(jià),在上述四種分離方法比選中,以蛋白酶解/膜分離組合法為佳。操作流程相對(duì)簡(jiǎn)單,分離率比較高,在分離回收戊聚糖的同時(shí)還可以進(jìn)一步得到氨基酸和還原糖。如果最終能夠?qū)崿F(xiàn)工業(yè)化,經(jīng)濟(jì)效益應(yīng)該比較高,所以應(yīng)用前景預(yù)期比較好。
[Abstract]:Wheat processing wastewater contains a large number of Recyclable, with high value of pentosan, protein and other organic matter, but the wheat starch processing plant will rarely pay attention to it, most of them are discharged into the sewage treatment station, and some even direct emissions. This is not only a waste of resources, but also cause serious pollution to the environment of wastewater treatment. The traditional methods such as evaporation, biological treatment, chemical treatment such as high energy consumption, long process, high processing cost, causing relatively heavy economic burden to the enterprise. The high recovery value of wheat wastewater treatment and resource utilization of low cost is a common problem of the whole industry. In this paper, by using the method of direct separation membrane separation exchange chromatography protein precipitation, membrane separation / enzyme combination method, four ways of protein / membrane separation combined method for separation and recovery of high value of pentosan from wheat starch wastewater, respectively. Experimental study on the root. According to the experimental results of the four methods to make transverse comparison, engineering for the recovery of Pentosans in wheat starch wastewater using reference. In addition, the monosaccharide composition of pentosans on spectral identification, detection of the degree of branching of the polymer. Direct membrane separation experiments show that when the liquid through 100m L interception 700m L, 10000Dalton (hereinafter referred to as Da) ultrafiltration membrane on Pentosan retention rate reached 97.81%, the protein retention rate reached 97.75%, the retention of these two substances and through the liquid concentration ratio were 15.29 and 10.48, showed that 10000Da membrane has good retention capacity of these two substances. Retentate while reducing sugar and amino acids and the permeate concentration ratio close to 1 indicates that the 10000Da ultrafiltration membrane without interception ability of reducing sugar and amino acids. The ultrafiltration experiments were performed with 20000Da and 50000Da membrane experiment, the number of According to the retentate protein and pentosan and the permeate concentration ratio is close to 1, indicated that the two kinds of membrane protein and pentosan are no interception function. The experiments with protease hydrolysis, thermal coagulation, bio flocculant, isoelectric point precipitation method, three chloroacetic acid flocculation method, five methods of pre removal the protein in Wheat starch processing, to provide a prerequisite for membrane separation and recovery of pentosan. The experimental results show that the removal of proteins are different. The removal rate of protein is enzymatic (87.11%) three trichloroacetic acid method (68.50%) natural polymer flocculation (20.29%) thermal coagulation (17.51%) isoelectric point method (8.56%). At the same time, pentosan five processing methods of the loss rates were: three trichloroacetic acid method (22.89%) protein (12.93%) organic polymer flocculation (11.21%) thermal coagulation (9.16%) isoelectric point method (8.24%). The protein removal The rate and pentosan retention rate as evaluation index, and ultimately determine the solution method for protein protease. The protease method suitable for wastewater pretreatment after protein removal rate was 87.11%, only subsequent loss of 12.93%. pentosan by direct membrane separation method, using 10000Da membrane, basically can be pentosan interception and recovery. On the basis of above experiments the experimental design method, enzymolysis and membrane separation combined: first for the decomposition of protein amino acids and then 10000Da ultrafiltration membrane amino acid, reducing sugar and pentosan enzyme / ultrafiltration separately. Experimental results show that when the liquid reaches to be separated through 1.5 times the volume of fluid (replenishment cycle), the whole process of protein the total removal rate is 92.27%, the reducing sugar and amino acids (protein digests) the retention rate of only 24.16% and 28.10%, the total pentosan retention rate of 77.36%.10000Da ultrafiltration membrane on reducing sugar and eggs White matter after degradation products of amino acids without interception function. Therefore, the cycle number increases, prolong the time of ultrafiltration can achieve the removal of protein hydrolysate in wastewater (amino acids) and reducing sugar, interception effect. This paper tries to pentosan exchange chromatography separation recovery of pentosan. Using DEAE-52 cellulose chromatography as medium, using water as eluent to join the amount of Na Cl enhanced segment elution effect. The eluate was analyzed by using the freeze-thaw judgment separation effect, analysis of protein content by UV spectrophotometry, ion chromatography quantitative analysis of pentosan (including reducing sugar). At the same time, auxiliary analysis to determine the chemical structure of solid component eluting liquid using infrared spectroscopy experiments. The results show that the distribution curve of pentosan in full compliance with the elution separation law of typical operation conditions of chromatography, separation is successful, DEAE-52 cellulose resin suitable for The separation of pentosan, good separation effect. Freeze detection results proved the most liquid chromatography elution in soluble pentosan and thawing method and ultraviolet spectrophotometry, impurities substantially free of protein and amino acid. The infrared spectra of 917.12 cm - 1 - D - galactose appear beta pyranose characteristic peak, 841.12 cm 1 alpha - D - Grape pyranose peaks, showed that the polysaccharide has a glycosidic bond and beta glycosidic bond. The recovered pentosan into monosaccharide by acid hydrolysis by ion chromatography detection of monosaccharide sugar belonging. Test results show that the wheat starch waste water separated from the main pentosan by the Arabia sugar, xylose, galactose and glucose,.N composed of four monosaccharides (Ara) /n (Xyl) ratio was 0.92, reflecting the degree of branching polymer pentosan is relatively large. The overall evaluation, the separation of the four methods is selected, by enzymatic hydrolysis Membrane separation / combination method is better. The operation process is relatively simple, the separation rate is relatively high, the separation and recovery of pentosan can also further amino acids and reducing sugar. If the final can achieve industrialization, economic benefits should be relatively high, so the application prospect is expected better.

【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：X792;TQ281

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