A spherical CuO-Bi2O3-MgO/SiO2 catalyst was prepared using the coprecipitation-gel method. The study investigated the influence of the MgO/SiO2 ratio on the catalyst structure and the activity of the catalyst in the preparation of 1,4-butanediol from formaldehyde acetylenation. The activity and filtration performance of the catalyst were compared with commercial samples. The study found that different MgO/SiO2 ratios not only changed the size of CuO particles, the orientation of crystal faces, the specific surface area, and the pore distribution in the catalyst, but also adjusted the interaction between CuO and SiO2. In addition, different MgO/SiO2 ratios could significantly alter the structure of the catalyst and enhance its activity, with the highest activity achieved when the MgO/SiO2 ratio was 1:3. Experimental results showed that the spherical CuO-Bi2O3-MgO/SiO2 catalyst in this study achieved a selectivity of 96.3% and a conversion rate of 94.0% when reacting with formaldehyde at a concentration of 38 wt% for 12 h. The catalyst outperformed commercial samples in terms of activity and had the same strength level and better filtration separation performance as commercial samples.

CuO-Bi2O3/SiO2@TiO2 core-shell structured catalysts were prepared by stepwise precipitation method and used for the synthesis of 1, 4-butynediol (BYD) by the ethynylation of formaldehyde. The characterization results, by XRD, BET, SEM, TEM, TPD etc., revealed the TiO2 content not only affecting the surface area of the catalysts and the partical size of the loaded CuO, but also affecting the electronic interactions with CuO. The activity tests showed that the catalyst with 20% TiO2 calcined at 450 degrees C had a short activation time, with good activity with conversion 91% and BYD yield 73% after 6 h on line. The catalysts still maintained good catalytic activity and stability after 6 repeated uses. ICP data indicate that leaching of Cu active component after reaction is very low.

The CuO-Bi2O3/MgAl2O4 catalyst was synthesized via one-pot synthesis and used to catalyze formaldehyde (HCHO) ethynylation. Coprecipitation using Cu2+, Bi3+, Mg2+, and Al3+ nitrates and NaOH generated Cu and Bi oxides and spinel MgAl2O4 phase. The catalyst precursor was calcined at 450 °C. The catalytic performance of CuO-Bi2O3/MgAl2O4 in the synthesis of 1,4-butynediol via HCHO ethynylation was investigated. The presence of a new spinel phase enhanced the acid-base properties on the catalyst surface and prevented the aggregation of CuO particles. These properties resulted in improved CuO dispersion during calcination and CuO particle growth suppression, affording smaller CuO crystals. The MgAl2O4 support facilitated the reduction of Cu2+ to Cu+ and formation of abundant active species during the reaction. The catalyst exhibited abundant weakly basic, fewer strongly basic, and least acidic sites, which facilitated the adsorption of HCHO and acetylene. The catalytic performance of CuO-Bi2O3/MgAl2O4 demonstrated 97 % conversion and 80 % selectivity after the online monitoring of the ethynylation reaction for 6 h. The leaching of Cu during the reaction, as analyzed by inductively coupled plasma spectroscopy, was extremely low. Moreover, conversion and selectivity did not substantially change after eight cycles. In addition, the catalyst exhibited superior activity and long-term stability in the ethynylation reaction.

A new antifreeze agent was prepared from Egg White Protein (EWP) and β-Cyclodextrin (β-CD). Through single factor experiments and response surface test, the preparation conditions of EWP-β-CD complex with the best antifreeze activity were obtained. Then EWP-β-CD complex with different concentrations (2%, 4% and 6%) was applied to the four freeze-thaw cycle system of shrimp to study the antifreeze protection of EWP-β-CD complex on shrimp. The results showed that the optimum conditions for the preparation of EWP-β-CD composite system were pH7.0, the composite ratio of β-CD and EWP 1:10, the heat treatment temperature 75 ℃. The antifreeze activity of EWP-β-CD composite system was 84.09%±1.06% under the optimal conditions. The EWP-β-CD complex under this condition was applied to the freeze-thaw cycle of shrimp. After adding EWP-β-CD complex, the water retention, hardness and chewability of shrimps were significantly improved, and the chromaticity of shrimps was not significantly affected. When the addition of EWP-β-CD complex was 4% and 6%, the effect of EWP-β-CD complex on protein degradation and fat oxidation of shrimp was significantly better than that of commercial antifreeze. The preparation conditions of EWP-β-CD complex are optimized by response surface method, and it was preliminarily showed that it had a certain protective effect on the quality of shrimp. This result would provide a theoretical basis for the subsequent development of low sweetness and low calorie antifreeze.

针对传统钴钼耐硫变换催化剂硫化过程带来的环境污染和安全问题,华烁科技股份有限公司研发了具有低活性温度的EB-6S系列中高压预硫化耐硫变换催化剂,介绍了其在河北正元氢能科技有限公司和潞安集团太化新材料有限公司变换装置中的应用情况.结果表明:EB-6S系列催化剂活性温度低至200℃,具有变换率高,稳定性好,蒸汽消耗低的特点.

以20～35 g克氏原螯虾为研究对象,随机分为4组,每组60尾,在基础饲料中分别掺拌0(C0组)、10(C10组)、20(C20组)、30 mg/kg(C30组)氟苯尼考喂养20 d,再改用基础饲料喂养15 d进行消除试验,测定肝胰腺Ⅰ相药物代谢酶7-乙氧基香豆素-O-脱乙基酶(ECOD)、7-乙氧基异吩恶唑酮-O-脱乙基酶(EROD)、苯胺-4-羟化酶(AH)、红霉素-N-脱甲基酶(ERND)、氨基比林-N-去甲基化酶(AND)和Ⅱ相药物代谢酶谷胱甘肽S-转移酶(GST)、磺基转移酶(SULT)、尿苷二磷酸葡萄糖醛酸转移酶(UGT)活力变化,以及细胞色素P450(CYP450)、GST、热休克蛋白HSP70和金属硫蛋白(MT)mRNA表达水平的变化.结果显示,氟苯尼考显著抑制Ⅰ相药物代谢酶活力,但能诱导Ⅱ相药物代谢酶活力升高(P<0.05).基因表达结果显示,氟苯尼考可诱导CYP450基因表达上调,10 mg/kg氟苯尼考可诱导GST基因表达上调,但20、30 mg/kg氟苯尼考对GST基因表达有抑制作用,基因表达水平与酶活力变化不一致的现象说明基因转录与蛋白质合成之间并没有必然的联系.10 mg/kg氟苯尼考通过诱导HSP70、MT等基因的表达维持机体的稳态,但高剂量氟苯尼考超出了机体的承受范围,引起机体损伤.消除试验结果表明,经过15 d的消除期后,除GST酶活力外,C10组其余药物代谢酶活力均恢复至正常水平,4种药物代谢基因表达水平也恢复至正常水平.为安全起见,以饲料掺拌方式饲养克氏原螯虾时,建议氟苯尼考剂量为10 mg/kg,既有利于充分发挥药效而不会过早排出体外,又可避免氟苯尼考剂量过高造成克氏原螯虾机体损伤和在体内蓄积.

研究光照、温度、氧化剂和还原剂对桑葚干和桑葚酒中花青素稳定性的影响,通过自由基清除试验评价桑葚干和桑葚酒的抗氧化能力,相关性分析讨论表征桑葚花青素稳定性的指标,比较桑葚花青素在不同产品中的稳定性.结果表明,桑葚酒中花青素对光照、温度、氧化剂、还原剂的耐受性显著强于桑葚干.桑葚酒提取物清除DPPH和ABTS+自由基的半数抑制率浓度均为3.05 mg/mL,对应的桑葚干提取物为3.93 mg/mL和3.55 mg/mL.相关性分析结果表明,光照、温度和H2O2对花青素的稳定性、花青素清除DPPH、ABTS+自由基能力与聚合型花青素占比成显著的正相关关系(p<0.05).表征花青素的稳定性指标可能是聚合型花青素所占比重,桑葚酒中花青素的稳定性强于桑葚干,更耐受复杂的外界环境变化.

为研究桑葚酒在4,25和45℃的贮藏温度下贮藏10 d后多酚类物质含量的变化情况,通过检测总酚含量、总黄酮含量、花青素保留率、羟基自由基清除率四个指标来确定桑葚酒的最佳贮藏温度.通过对桑葚酒进行热处理,检测桑葚酒在60,70和80℃的温度下花青素保留率随加热时间的变化规律.结果 表明:桑葚酒适宜在25℃的贮藏温度下贮藏;桑葚酒在热处理过程中的花青素保留率随热处理温度的提高和加热时间的延长而下降,桑葚酒中花青素热降解动力学模型符合一级反应规律,动力学方程为t=(lnC0-lnC1)/[(1.71×105)×exp(-5 014.43/T).此次研究为桑葚酒的贮藏和生产开发提供了一定理论基础.

为确定pH示差法测定桑葚酒中花青素的最佳测定条件,本文对pH示差法测定桑葚酒中花青素含量的最佳测定波长、缓冲液的最适pH、平衡温度和时间等条件进行优化,并且对优化的pH示差法进行方法学评价.结果 表明,在波长519 nm、缓冲液pH为1.0和4.5、于30℃下恒温40 min后测定桑葚酒中花青素含量是最佳的条件.测定桑葚酒中花青素的含量为23.80 mg/L.该方法的相对标准偏差(RSD)为2.076％,加标回收率为99.59％～102.70％,说明用优化后的pH示差法测定桑葚酒中花青素含量是准确可靠的.本文为酒为存在介质的花青素定量分析提供了借鉴.

以面粉、油、糖为主要原料制作曲奇饼干,通过测量其水分含量、色度、质地、感官和丙烯酰胺含量,研究原料特性对曲奇饼干品质和丙烯酰胺生成的影响.实验表明:面粉中蛋白质的含量显著影响曲奇饼干的品质和丙烯酰胺的生成.与高筋粉和中筋粉相比,低筋粉粗蛋白含量仅为7.67％,其制作的曲奇饼干水分含量低,硬度小,柔软和酥松程度表现更好,品质最佳且丙烯酰胺生成量最低.普通黄油和发酵黄油制作的曲奇饼干酥脆,香味浓郁,品质优良,发酵黄油在焙烤过程脂肪氧化较为缓慢,生成的丙烯酰胺含量低为212 μg/kg.红糖制作的曲奇饼干呈棕褐色,具有独特的香味,但丙烯酰胺含量高达828 μg/kg.白砂糖、冰糖和绵白糖制作的曲奇饼干品质差异较小,其中白砂糖制作的曲奇饼干感官评价得分最高,丙烯酰胺含量最低为230 μg/kg.综上,低筋面粉、发酵黄油和白砂糖制作的曲奇饼干品质较优,丙烯酰胺生成量较少.

介绍了与6.5 MPa水煤浆气化工艺相匹配的绝热变换和控温变换两种变换工艺,对比了两种变换工艺的工艺流程、设备、催化剂、投资和运行情况等.结果 表明:与绝热变换工艺相比,控温变换工艺流程简单,操控方便,设备数量少,占地面积小,催化剂使用数量少约20％,催化剂使用寿命延长约2a,投资约为绝热变换的50％.

雷尼镍是一种被广泛用于多种化工过程的催化剂,将雷尼镍催化剂应用于固定床反应器,能拓宽其在加氢精制领域的应用,同时可降低操作和分离成本.介绍了几种固定床雷尼镍催化剂,并对其优缺点进行比较.

针对铁钼法甲醛生产工艺进口催化剂国外技术垄断、价格昂贵的现状,自主研发了EQ-101型铁钼甲醛合成催化剂,并进行了工业应用.介绍了EQ-101型甲醛催化剂的物性指标及催化剂装填情况;分析了采用该催化剂后开车阶段和工业运行阶段甲醛产品质量和ECS入口尾气副产物等工艺指标.结果表明,甲醛产品质量和ECS入口尾气副产物各项指标可满足工艺要求,生产1t质量分数37％的甲醛平均甲醇单耗约430 kg,甲醛收率92％,甲醇转化率98％,与进口催化剂水平相当,具备工业推广条件.

介绍了治理氯的重要性及必要性.综述了煤炭及原油中氯的赋存形态:煤炭中氯的赋存形态主要是无机氯化物;石油中氯的赋存形态可分为无机氯化物及有机氯化物,其中原油开采过程中加入的含有机氯的油田化学助剂是原油中有机氯的主要来源.分析了煤层及石油中氯的危害性:煤层及石油中存在的氯主要会导致设备管道的腐蚀、堵塞及催化剂失活;能源开采特别是石油开采过程中减少含氯开采助剂的使用及开发无氯助剂可以从源头上减小氯的危害性,该分析结果可以有针对性地控制氯含量有指导意义.

介绍了适用于淤浆床工艺、醛炔法生产1,4-丁炔二醇的EQ-201型炔化催化剂的物性指标,并测试了其活性.将该催化剂在新疆天智辰业一期1,4-丁二醇装置进行了工业应用,结果表明:该催化剂的甲醛转化率、产物电导率、产物中丙炔醇、二氧化硅、铜和未知物等各项指标都达到了国外同类催化剂的水平.对使用后该催化剂样与国外催化剂样进行了扫描电镜(SEM)分析,发现两者的磨耗情况没有明显区别.该催化剂具备工业推广条件.

In order to improve the activity of the sulfur-tolerant catalyst for methanation, NSM-42 Ni-Mo based methanation catalysts had been developed by Haiso Technology Co., Ltd. and these catalysts had performance test at the atmospheric tubular reaction evaluation device. The effects of reaction temperature, space velocity, feed ratio and other operating conditions on the performance of NSM-42 catalyst were tested, and then 30 h life test was made on the improved NSM-43 catalyst. The test results showed that with the increase of reaction space velocity, the reaction activity of NSM-42 catalyst was decreased; the catalyst exhibited high methanation activity with the reaction temperature between 350℃and 400℃, catalyst calcination temperature at 375 ℃ and high carbon hydrogen ratio. For NSM-43 catalyst, in the first 20 h of reaction, the CO conversion rate was up to 99% and the CH4 selectivity was up to 78%.

采用气质联用仪、电子鼻和质构仪等仪器比较茶多酚、姜汁料酒及二者组合脱除白鲢鱼腥味物质的同时对鱼糜风味、鱼肉营养成分和口感的影响,以期建立一种保持鱼肉原始风味和口感的新型脱腥方法.结果表明:与对照相比,经过3种方法处理后的腥味物质的种类和含量均明显减少,其中茶多酚姜汁料酒组合时脱腥效果最好,3种评价结果基本吻合,脱腥后的鱼糜无鱼腥味,而且营养和卫生指标均符合国家标准.

利用纯物质热化学数据对甲醇工况中的Fe(CO)5平衡浓度进行了热力学计算.计算结果表明在在常温条件下倾向于生成Fe(C0)5,在甲醇合成条件下Fe(CO)5分解倾向于自发发生;在热力学上,Fe(CO)5分解反应在300K以上温度条件下均为自发过程.

华烁科技股份有限公司采用共沉淀法制备了铜锌系新型羰基金属净化剂.在常压条件下,相对固定评价条件,分别考察反应温度、空速、入口Fe(CO)5含量、CO含量等因素对净化剂铁容的影响.实验表明,新型羰基金属净化剂用于甲醇合成原料气净化,在甲醇合成工况下,反应管出口羰基金属含量<0.1×10-6、铁容≥4.5%,完全可用于甲醇合成原料气的深度净化.