氧肟酸基团含量高的改性絮凝剂制备及应用

以高分子量聚丙烯酰胺(PAM)为原料,合成了聚丙烯酰胺改性氧肟酸型絮凝剂产品(HPAM)。通过傅里叶变换红外光谱分析(FT-IR)证实了该产品中氧肟酸基团的存在。用电导滴定法与凯氏定氮法相结合,测得该产品中氧肟酸基团含量高达46%,羧基含量23%。用针铁矿含量高的合成拜耳法赤泥浆料研究了该絮凝剂产品添加量对针铁矿含量高的赤泥沉降分离效果影响。结果表明,该絮凝剂产品对于该针铁矿含量高的赤泥具有良好的沉降分离效果,与美国氰特公司产品Hx-600的赤泥沉降效果基本相当。

含氧肟酸基团絮凝剂的合成及其对赤泥的沉降效果

本文以自制高分子量的聚丙烯酸为原料,1,4-二氧六环为溶剂,用N,N’-羰基二咪唑在100℃下活化聚丙烯酸5h,然后再加盐酸羟胺在一定温度下(30～50℃)反应一定时间(5～24h),得到了含氧肟酸基团的絮凝剂产品。通过与FeCl3显色反应、红外光谱分析表明了产品中氧肟酸基团的存在,用凯氏定氮法测得产品中氧肟酸基团含量高达57.5%。所得产品对于针铁矿含量高的赤泥具有良好的沉降效果:赤泥浆液固含量为42g/L,产品添加量为240ppm时,前5分钟平均沉降速度为1.75m/h,沉降30min后上清液浊度为596NTU。而聚丙烯酸钠、ALCLAR665和Nalco9779商品絮凝剂的沉降效果却很差。

Flocculation performance and mechanism of hydroxamate flocculants on synthetic hematite or goethite suspension

Suitable amounts of Al(OH)3, Na OH and synthetic hematite or goethite were taken to be digested under the simulated condition of the Bayer process and subsequently diluted with simulative Bayer red mud lotion, then the synthetic hematite or goethite suspension was obtained. The flocculation effect of self-made modified poly(acrylic acids) flocculants containing hydroxamic acid groups(abbreviated as HPAA) on the synthetic hematite or goethite suspension was studied. The experimental results show that with the increase of the dosages of added flocculants, the average settling rate of the synthetic hematite or goethite suspension in the first 1min speeds up, the supernatant solids decrease. It could also be found that there is generally a decrease in the average settling rate of the synthetic hematite or goethite suspension in the first 1 min with increasing solid content of the suspension. When the solid content of hematite or goethite of the suspension is 50 g/L with 240 g/t dosage of HPAA, HPAA has a better flocculation effect on the synthetic goethite suspension than on the synthetic hematite suspension. The adsorption mechanism of HPAA on the surface of hematite or goethite was investigated by Fourier transform infrared spectroscopy(FT-IR) and X-ray photoelectron spectroscopy(XPS).All the results suggest that HPAA is adsorbed on the hematite or goethite surface by a chemisorption, and it has a stronger adsorption on the goethite surface than on the hematite surface.

Synthesis of modified polyacrylamide with high content of hydroxamate groups and settling performance of red mud

Hydroxamated polyacrylamide(HPAM) was synthesized from polyacrylamide(PAM) with high relative molecular mass under the optimum reaction conditions(p H 12 and a molar ratio of hydroxylamine to amide groups of 1.5 at 50 °C for 12 h). The hydroxamate groups of HPAM were verified by Fourier transform infrared spectrum(FT-IR). 46%(molar fration) hydroxamate groups and 23%(molar fraction) carbonyl groups on HPAM were determined by conductometric titration combined with Kjeldahl's microanalysis method. The settling performance achieved at different flocculant dosages was investigated with high goethite-containing red mud slurry of simulated Bayer process synthesized in laboratory. It turns out that the settling performance of high goethite-containing red mud was better with HPAM. The average settling rate of red mud in the first 5 min and the turbidity of supernatant after settling for 30 min are 2.36 m/h and 507 NTU, respectively, at a flocculant dosage of 120 g/t, which is similar to that achieved with Hx-600.

Flocculation Mechanism of Synthetic Goethite Suspension Using Hydroxamated Polymer and Sodium Polyacrylate

The flocculation effects of homemade hydroxamated flocculant(HPAA)and commercially available sodium polyacrylate(PAAS)on synthetic goethite suspensions with different solid contents were studied.The adsorption mechanism of HPAA or PAAS on the surfaces of goethite was investigated.The settling rate of 50 g/L goethite suspension with HPAA(1.74 m/h)was faster than that with PAAS(0.54 m/h),which indicated that HPAA exhibits better flocculation performance than PAAS does.It could be found that the stretching vibration of carbonyl band in hydroxamic acid groups of HPAA was downshifted from 1 654 cm^(-1) to 1 645 cm^(-1) and a new adsorption band appeared at 1 455 cm-1,which demonstrated that a five-membered ring chelate may be formed among iron atoms of goethite surfaces,the hydroxyl groups and the carbonyl groups in hydroxamic acid groups of HPAA.In the case of PAAS,the separation of the asymmetric and symmetric stretches of the carboxylate groups in adsorbed PAAS was 163 cm-1,which was greater than that of unadsorbed PAAS with 157 cm^(-1).There was no indication of a contribution from the monodentate adsorption between iron atoms of goethite surfaces and carboxylate groups of PAAS,but there may exist a bi-dentate bridging structure.Compared with synthetic goethite,XPS curve fittings of Fe 2p spectra showed that the binding energies of the main Fe 2p3/2 and Fe 2p1/2 resolved peaks on HPAA-treated goethite surfaces were correspondingly decreased by 0.9 and 0.7 e V,while those on PAAS-treated goethite surfaces were correspondingly decreased by 0.7 and 0.3 e V.The characteristic N 1s peak of HPAA and C 1s peak of PAAS were correspondingly detected on HPAA-treated and PAAS-treated goethites,and a binding energy change of N 1s spectrum of adsorbed HPAA was observed.The relative atomic ratios of C/Fe,N/Fe and O/Fe on HPAA-treated and PAAS-treated goethite surfaces were increased.All the results suggested that HPAA or PAAS was adsorbed on the goethite surfaces by the chemisorption,and a stronger adsorption of HPAA on the goethite surfaces happened than that of PAAS.