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1、 目 录1英文文献翻译11.1英文文献原文（原文题目）11.2 中文翻译92. 专业阅读书目152.1 当代废纸制浆技术152.2 制浆原理与工程152.3制浆造纸污染控制162.4 加工纸与特种纸162.5 造纸湿布化学172.6 再生纤维与废纸脱墨技术172.7制浆造纸工程设计182.9 造纸化学品的制备和作用机理192.10造纸原理与工程19 1 英文文献翻译1.1 Inorganic Reactions in Chlorine Dioxide Bleaching of Softwood Kraft PulpINTRODUCTIONDue to environmental concern

2、s, elemental chlorine is being replaced withchlorine dioxide (ClO2) for the bleaching of wood pulps. Chlorine dioxideis a very selective bleaching reagentpresence of carbohydrates, thereby preserving pulp quality. In addition, ClO2generates less chlorinated organics or adsorbable organic halides (AO

3、X)compared to chlorine, increasing the attractiveness of chlorine dioxide as ableaching reagent. However, there are issues surrounding the utilization ofchlorine dioxide. Based on oxidation equivalents it is more expensive thanelemental chlorine. Furthermore, the formation of chlorate and chloritede

4、crease its oxidation efficiency, further increasing the cost of bleaching.One of the keys to optimizing a chlorine dioxide bleaching stage is tominimize the formation of chlorate and chlorite. In the past, chlorinedioxide bleaching studies on chlorine pre-bleached pulps have shown thatthe optimal us

5、age of chemical (minimum chlorate and chlorite residues)requires that the end pH be around 3.8.1 However, this may not be true forchlorine dioxide pre-bleaching because residual kraft lignin componentsmost likely differ from the residual lignin in a chlorine pre-bleached pulp. Ithas been shown that

6、lignin structure, particularly phenolic lignin content,directly influences the bleachability of wood pulps.2,3 Therefore, prebleachingwith chlorine dioxide may require different reaction conditions tominimize chlorite and chlorate formation. In this article we report the effectof end pH on the forma

7、tion of inorganic chlorine species during chlorinedioxide pre-bleaching of a softwood kraft pulp.EXPERIMENTALMaterials3,4-Dimethoxyacetophenone, sodium borohydride (NaBH4), p-dibromobenzene,biphenyl, and all solvents were purchased from Aldrich Chemicals and used asreceived. Chlorine dioxide was pro

8、duced by reacting 80% stabilized sodiumchlorite (ACROS) with 1.5 equivalents of potassium persulfate (Fluka) indistilled water at room temperature. The resulting solution was stripped withUHP-nitrogen. Nitrogen gas containing stripped chlorine dioxide was passedthrough a column of sodium chlorite (A

9、ldrich), then scrubbed in coldHPLCwater.Methylveratrylalcohol (MVA) was prepared by reacting 3,4-dimethoxyacetophenonewith 2 equivalents of NaBH4. The reaction mixture was refluxedin 3 : 1 MeOH :H2O for 3 h, neutralized with carbon dioxide, and extractedwith 1,2-dichloroethane. Quantitative conversi

10、on of the acetophenone wasobtained. MS m/z (rel. int.) 182(Mt, 59), 167(87), 153(47), 139(100),124(32), 108(21), 93(50), 77(21), 65(25), 51(11), 43(41). 1H-NMR d1.48(d,3H), 3.90(d,6H), 4.83(q,1H), 6.84(q,1H), 6.86(q,1H), 6.93(d,1H).Chlorine Dioxide Reactions with PulpThe 27 kappa softwood kraft pulp

11、 (12 g OD) was prebleached with chlorinedioxide using a 0.2 kappa factor. The bleaching was carried out at 10% consistencyat 508C for 2 h. The initial pH of the pulp was adjusted using aqueoussodium hydroxide (5 wt%) or sulfuric acid (5 wt%) to achieve a desired finalpH. HPLC grade water (Aldrich) w

12、as used as the makeup water. Polyethylenebags fastened with rubber septa were used for bleaching. Samples forinorganic ion analysis were prepared by injecting 20 mL effluent samplesinto a 7 mL vial and evacuating for 45 s, a 1 mL aliquot of HPLC waterwas then added to the sample, followed by the add

13、ition of a sodium fluorideinternal standard. Effluent samples were taken periodically during the 2 hbleach. Ions were analyzed using an ion-exchange column (Dionex AS9/AG9 guard column) with 2.5 mM sodium borate eluent. The eluent flowrate was 1.75 mL/min. Chemical detection was done by suppressed c

14、onductivityusing a Dionex CD20 conductivity detector. Chlorine dioxideconcentrations were determined by iodometric titration. The quantity ofhypochlorous acid in the reaction medium was determined by trapping withaqueous solutions of dimethylsulfoxide (DMSO). Samples (100 mL) of thereaction mixture

15、were injected into 0.5 mL of cold aqueous solutions containingexcess DMSO (0.25 M, pH adjusted to 8). Trapped samples werequenched after 15 s with a saturated sodium thiosulfate solution. Theresulting dimethylsulfone content was determined by GC using cyclohexanolas an internal standard.Chlorine Dio

16、xide Reactions with MVAMVA reactions were run at 25+18C in an oil bath as previously reported.4The pH of the chlorine dioxide reaction was kept constant by using a pHcontrol feedback loop. Reactions were run in a 100 mL, 4-necked flask. AnOmegaTMpH controller (model PHCN-37) was connected to a Milto

17、n-Roymicro-chemical metering pump (model A771-155S). A sodium hydroxideolution (0.8 M) was delivered to the reaction vessel from a burette viaNalgenew PVC tubing. The alkali addition did not exceed 1% of the totalreaction volume. The reaction mixture was stirred magnetically with aTeflon coated bar.

18、 The pH of the water and chlorine dioxide were adjustedusing aqueous sodium hydroxide (5 wt%) or sulfuric acid (5 wt%) toachieve the desired final pH and mixed for one minute prior to injection ofan aqueous solution of MVA. Samples of the reaction were taken with asyringe through a rubber septum. In

19、 the kinetic experiments sampling wasdone until all MVA or chlorine dioxide was consumed.Organic compound concentrations were determined by gas chromatography.Twenty mL samples of the reaction mixture were quenched eitherby adding 0.5 mL of 0.4 M ascorbic acid or 0.5 mL of a saturated aqueoussodium

20、thiosulfate solution. The quenched samples were extracted with0.5 mL of ethyl acetate containing 0.6 mg/L p-dibromobenzene or biphenylas an internal standard. Thereafter, the samples were dried over anhydroussodium sulfate and made up to 2 mL with ethyl acetate prior to GC analysis.GC analyses were

21、performed on an HP 5890 (splitless injection) instrumentequipped with a flame ionization detector, using He as the carrier gas.Injector and detector temperatures were 2408C and 2808C, respectively. Separationswere achieved on a J&W DB-5 fused silica capillary column(30 m 0.32 mm 0.25 mm). Typical te

22、mperature programs were from458C to 2508C at a rate of 108C/min with an initial time delay of 1 min,and from 1008C to 2708C at 10208C/min. In quantitative studies, pdibromobenzeneor biphenyl was used as an internal standard and therelative peak areas and corresponding response factors were used toca

23、lculate concentrations.All GCMS analyses were conducted using the GC analysis conditions ona HP 5985B GCMS equipped with a DB-5 capillary column. In the EI mode,the electron energy used was 70 eV.1H-NMR spectra were determined on a GE 300 MHz instrument. Sampleswere dissolved in CDCl3. Chemical shif

24、ts are given in ppm downfield fromTMS (tetramethylsilane).RESULTS AND DISCUSSIONA 27 kappa softwood kraft pulp was bleached with chlorine dioxide (ClO2) tovarious end pH values. The quantity of chlorite (ClO22), chlorate (ClO32), andchloride (Cl2) were determined as a function of reaction time and a

25、re shownin Figures 1 and 2.During high pH bleaching (pH 11.2), chlorite formed rapidly. The firstsample point (3 min) for the pH 11.2 reaction shows that approximately70% of the chlorine dioxide had been converted to chlorite. At this pH thechlorite concentration did not change significantly (Figure

26、 1A). However, asthe end pH dropped, chlorite degradation began to occur (Figure 1B1D).The rate of chlorite consumption appeared to increase with a decrease inbleaching pH. As a result, less residual chlorite was measured after 120 minof bleaching with decreasing end pH. By contrast, chlorate and ch

27、lorideBleaching EfficiencyFinal analysis of inorganic compounds in the bleach effluent shows thatbleaching to an end pH of less than 3.4 results in the most efficient usage ofchemicals. As shown in Figure 3 the amount of residual chlorite t chloratedecreases with end pH until about 3.4. Below an end

28、 pH of 3.4, the quantityof residual chlorite t chlorate levels out. This observation is different thanthat reported by Chollet et al.,11 who found that bleaching a chlorine prebleachedpulp (Kappa no. 5) with chlorine dioxide gave the minimumchlorate t chlorite levels at an end pH of between 3 and 4.

29、 In addition, themaximum pulp brightness was attained around an end pH of 3.8. InChollets study the quantity of chlorine dioxide lost to chlorate was shownto increase dramatically with decreasing pH below 3. Under acidic conditionschlorate is formed according to Equation (10). Under our conditions,

30、theamount of chlorite that is available to participate in this reaction is likelylower than that in Chollets system due to the higher lignin content of ourpulp. The higher lignin content corresponds to a larger amount of phenolicmoieties (the phenolic hydroxy content of a 30 kappa softwood kraft pul

31、p isapproximately between 20 to 30% of the residual lignin12,13), resulting ina much lower concentration of chlorite available to participate in Equation(10).Brightness and permanganate number trends appear to correlate with theamount of residual chlorite t chlorate. Figure 7 shows that decreasing e

32、nd pHbelow 3.4 did not have a significant effect on the brightness or the permanganatenumber after an extraction stage; however, the organic chlorine levelCONCLUSIONSPre-bleaching a 27 kappa softwood kraft pulp with chlorine dioxide wasperformed to various end pH levels. During high pH bleaching, th

33、e majorityof the bleaching chemicals were lost to chlorite formation. The rapidoxidation of the phenolic lignin results in the formation of chlorite and hypochlorousacid, but the oxidation of non-phenolic lignin at high pH forms onlychlorite. Without the presence of the hypochlorous acid formed from

34、 thereaction with the non-phenolic lignin moieties, chlorine dioxide is not regeneratedand further reaction with lignin and the residual chlorite does not occur.Further, chlorite is ionized at high pH, which prevents it from undergoing disproportionation.Therefore, at high pH chlorite remains fairly

35、 stable, resultingin a loss in oxidation efficiency.Decreasing end pH (,6) resulted in a greater amount of chlorite degradation.At low pH the reaction of chlorine dioxide with non-phenolic ligninmoieties formed both chlorite and hypochlorous acid. The hypochlorousacid then reacts with chlorite to re

36、generate chlorine dioxide or reacts withlignin to form organic chlorine. Lignin oxidation by chlorine dioxidefollowed by chlorine dioxide regeneration by hypochlorous acid continuedREFERENCES1. Rapson, H.W.; Strumila, G.B. Bleaching of Pulp; TAPPI Press: Atlanta, GA, 1979;113157.2. Kumar, K.R.; Jaco

37、bs, C.; Jameel, H.; Chang, H.-M. International Pulp BleachingConference. TAPPI Proceedings, 1996; 147152.3. Germgard, Ulf. TAPPI J. 1982, 65 (12), 8183.4. Svenson, D.R.; Kadla, J.F.; Chang, H.-M.; Jameel, H. Can. J. Chem. 2002, 80,761766.5. Brage, C.; Eriksson, T.; Gierer, J. Holzforschung 1991, 45

38、(1), 2330.6. Hoige, J.; Bader, H. Water Research 1994, 28 (1), 4555.7. Kieffer, G.; Gordon, G. Inorg. Chem. 1968, 7 (2), 239244.8. Emmenegger, F.; Gordon, G. Inorg. Chem. 1967, 36 (3), 633635.9. Hong, C.C.; Rapson, W.H. Can. J. Chem. 1968, 46, 20532060.10. Hong, C.C.; Rapson, W.H. Can. J. Chem. 1968

39、, 46, 20612064.11. Chollet, J.L.; Leduc, P.B.; Renault, H. Pulp and Paper 1960, 34 (6), 64.12. Gellerstedt, G.; Lindfors, E. Svensk Papperstidn. 1984, 15, R115R118.13. Lai, Y.-Z.; Mun, S.-P.; Luo, S.-G; Chen, H.-T.; Ghazy, M.; Xu, H.; Jiang, J.E.Holzforschung 1995, 49, 319322. 1.2中文翻译 在针叶木硫酸盐浆漂白中二氧化

40、氯的无机反应 引言 由于环境问题，氯元素被替换为 二氧化氯（ClO2）对木材纸浆的漂白。二氧化氯 是非常有选择性的漂白剂，优选氧化木质素。碳水化合物的存在，从而保持纸浆的质量。另外，二氧化氯产生更少的含氯有机物或可吸附有机卤化物（ AOX ）相比于氯，增加作为二氧化氯的吸引力漂白剂。但是，也有周围的利用问题二氧化氯。基于氧化当量它比更昂贵的元素氯。此外，氯酸盐和亚氯酸盐的形成降低其氧化效率，进一步提高漂白的成本。一个键来优化一个二氧化氯漂白阶段的是对减少氯酸盐和亚氯酸盐的形成。在过去，氯对氯预漂白纸浆漂白的二氧化研究表明化学品的最佳使用（最低氯酸盐和氯酸盐残留物）要求最终pH值约为3.8 。

41、1然而，这未必是真实的二氧化氯预漂白，因为残留的牛皮纸木质素成分从在氯预漂白纸浆的剩余木素最有可能不同。它已经表明，木质素结构，特别是酚类木质素含量，直接影响木材纸浆的漂白性2,3因此，预漂白用二氧化氯可能需要不同的反应条件下，以减少亚氯酸盐和氯酸盐的形成。在这篇文章中，我们报告的影响无机氯物种的氯气中的形成端部的pH二氧化预漂白软木牛皮纸浆实验物料3,4 - 二甲氧基苯乙酮，硼氢化钠（硼氢化钠），对 - 二溴苯，联苯，和所有的溶剂均购自Aldrich Chemicals ，并用作接收。二氧化氯是由反应产生的80 的钠稳定绿泥石（ ACROS ）与1.5当量的过硫酸钾（ Fluka公司）在蒸馏

42、水在室温下。将所得溶液用剥离超高压氮。含有剥离二氧化氯的氮气通过通过亚氯酸钠（ Aldrich公司）的列，然后擦洗的coldHPLCwater 。Methylveratrylalcohol （ MVA）反应，制备3,4 - 二甲氧基苯乙酮与2当量的NaBH 4 。将反应混合物回流在3:1的MeOH ：H 2 O为3小时，用二氧化碳，并提取用1,2 - 二氯乙烷。苯乙酮的定量转化率是获得的。 MS M / Z （相对强度） 182 （ MTH ， 59 ） ， 167 （ 87 ） ， 153 （ 47 ） ， 139 （ 100 ） ，124 （32 ），108（ 21 ），93（ 50 ），

43、77（ 21 ），65（ 25 ），51（ 11 ），43（ 41） 。 1 H-NMR 1.48 （四，3H）， 3.90 （四，6H）， 4.83 （Q， 1H），6.84 （Q， H）， 6.86 （Q， 1H），6.93 （D， 1H）。二氧化氯反应与纸浆27卡帕软木牛皮浆（12克OD）是prebleached用氯二氧化使用0.2卡伯因子。漂白反应在10 稠度在508C 2小时。使用水性纸浆的初始pH值调节氢氧化钠水溶液（ 5重量 ）或硫酸（ 5重量 ），以实现期望的最终pH值。 HPLC级水（ Aldrich）用作作为化妆水。聚乙烯袋固定用橡胶隔片被用于漂白。样本无机离子分析，制备了

44、注射20毫升污水样本到7毫升小瓶和疏散45秒，高效液相色谱水1毫升分装、然后，加入到样品中，随后通过加入氟化钠内标。污水样品的2小时内采取定期漂白剂。使用离子交换柱（ Dionex公司AS9 /离子进行分析AG9保护柱）用2.5 mM的硼酸钠淋洗液。洗脱流率为1.75毫升/分钟。化学检测是通过抑制电导完成使用戴安CD20电导检测器。二氧化氯浓度用碘量滴定法测定。数量次氯酸在反应介质中通过用截留确定二甲基亚砜（DMSO）的水溶液。的样品（100mL）中反应混合物分别注入0.5毫升含冷水溶液过量的DMSO （0.25M ，pH值调节至8 ） 。被困样本15秒钟后，用饱和的硫代硫酸钠溶液骤冷。该产生

45、的二甲基砜含量用气相色谱用环己确定作为内标物二氧化氯反应与MVA的反应均在25 18下在如先前报道的油浴中运行。 4二氧化氯的反应的pH值保持恒定，使用pH控制反馈回路。反应在100mL四颈烧瓶运行。一个欧米茄商标pH值控制器（型号PHCN -37）被连接到一个米尔顿罗伊微化学计量泵（型号A771 - 155S ） 。氢氧化钠溶液（ 0.8 M）经由输送到反应容器中从滴定管Nalgenew PVC管。碱加成不超过总量的1的反应体积。将反应混合物在磁力搅拌与aTeflon涂覆棒。水和二氧化氯的pH值分别调整用氢氧化钠水溶液（ 5重量 ）或硫酸（ 5重量 ），以达到所需的最终pH值，混合注射前一分

46、钟MVA的水溶液。该反应的样品取自同一个注射器通过橡胶隔膜。在动力学实验采样是这样做，直到所有的MVA或二氧化氯被消耗。有机化合物的浓度用气相色谱法测定。将反应混合物的二十毫升样品进行淬灭或通过加入0.5ml的0.4M的抗坏血酸或0.5毫升的饱和水溶液硫代硫酸钠溶液。淬火样品的提取0.5毫升乙酸乙酯含有0.6 mg / L的对 - 二溴苯，联苯作为内标物。此后，将样品用无水干燥并制成高达2之前， GC分析毫升，用乙酸乙酯洗涤。GC分析在HP 5890 （不分流进样）进行仪器装有火焰电离检测器，使用He作为载气。注射器和检测器温度分别为2408C和2808C分别。分离在JW DB - 5石英毛细

47、管柱分别实现（30米？ 0.32毫米0.25毫米）。典型的温度方案是从458C到2508C在108C/min的为1分钟的初始时间延迟的速率从1008C到2708C在10-208C/min 。在定量研究， pdibromobenzene或联苯作为内部标准和相对峰面积和相应的响应因子被用于计算浓度。所有的GCMS分析采用的气相色谱分析条件进行一台HP 5985B GCMS配有DB- 5毛细管柱。在EI模式下，所使用的电子能量为70电子伏特。1 H- NMR谱是在GE 300 MHz的仪器测定。样品溶解在CDCl 3中。化学位移以从给定的ppm低磁场TMS（四甲基硅烷） 。结果与讨论 阿27卡巴针叶

48、木硫酸盐纸浆漂白用二氧化氯（ClO2）来 各种终端的pH值。绿泥石的数量（二氧化氯 2），氯酸根（CLO3 2），以及 氯（CL2）进行了测定，作为反应时间的函数，并示 在图1和图2。 在高pH漂白（pH值11.2），绿泥石迅速形成。第一 采样点（3分）为pH值11.2的反应表明，约 二氧化氯的70已被转化为绿泥石。在此pH值的 亚氯酸盐浓度并没有显著改变（图1A）。然而，如 年底pH值下降，绿泥石降解开始出现（图1B-1D）。 绿泥石消耗速率似乎增加与减少 漂白pH值。其结果是，较少的残余亚氯酸盐是120分钟后测得 漂白与减少年底pH值。相比之下，氯酸盐和氯化物漂白效率在漂白废水的无机化合物的最终分析表明，漂白至小于3.4的结果中的最有效的