NH~+_4,K~+//H_2PO~-_4,CO(NH_2)_2-H_2O四元体系298.15K相平衡研究

采用等温溶解平衡法研究了三元体系NH_4H_2PO_4-CO(NH_2)_2-H_2O和四元体系NH~+_4,K~+//H_2PO~-_4,CO(NH_2)_2-H_2O在298.15 K下的固液相平衡关系。通过湿渣法与X射线衍射相结合的方法鉴定了平衡固体组成,绘制了298.15 K下该三元体系的平衡相图以及该四元体系的平衡相图和水图。研究结果表明:三元体系NH_4H_2PO_4-CO(NH_2)_2-H_2O在298.15 K时相图中有1个共饱和点、2条单变量曲线、4个区域[分别对应NH_4H_2PO_4和CO(NH_2)_2的共结晶区,NH_4H_2PO_4结晶区,CO(NH_2)_2结晶区,不饱和区]。四元体系NH~+_4,K~+//H_2PO~-_4,CO(NH_2)_2-H_2O在298.15 K时相图中有1个共饱和点、3条单变量曲线、3个结晶区[分别对应CO(NH_2)_2结晶区,(NH_4,K)H_2PO_4固溶体结晶区,(K,NH_4)H_2PO_4固溶体结晶区]。实验结果可为该体系的共结晶研究提供必要的溶解度数据。     

双核羧酸钼Mo_2(OCOR)_4合成的研究

对双核羧酸钼的氧化聚合法进行了考察,优化了合成条件。Mo_2(OCOCH_3)_4、Mo_2(OCOC_3H_7)_4、Mo_2(OCOC_4H_(?))_4和 Mo_2(OCOC_(?)H_5)_4的产率分别为57.02%、48.90%、38.90%和67.10%。提出了可能的反应机理。研究发现,使用一定配比的苯与乙醚的混合溶剂且在水解时加铁,有助于 Mo(CO)_(?)产率的提高。Mo(CO)_(?)的产率为43.8%。     

尿素—纯碱—氯化铵联合生产工艺研究(第二报)——(NH_2)_2CO—NH_4Cl—NaCl—H_2O四元体系相图

(NH_2)_2CO—NH_4Cl—NaCl—H_2O四元体系相图本文第1报曾于报导,碳酸化母液中含(NH_2)_2CO、NH_4Cl、NaCl、NH_(?)HCO_3。如用加热办法将NH_(?)HCO_3分解除去,则母液就成了(NH_2)_2CO—NH_(?)Cl—NaCl—H_2O四元体系。为了进一步探讨从中制取(NH_2)_2CO—NH_4Cl混合肥料的可能性和寻求其最适宜的操作条件,特研究了这一四元体系的100℃、35℃及15℃三种温度的相图。通过对此四元体系相图的研究,作者分析了各种温度下分离混合肥料的情况。     

Al(OH)_3阻燃聚丙烯塑料

本文介绍了阻燃剂Al(OH)_3的阻燃机理及Al(OH)_3阻燃PP塑料的工艺、配方、性能和应用,并对它的技术经济作了评价。     

Fe(CO)_5为原料合成几种铁羰基化合物

以Fe(CO)5为起始原料直接或间接合成了Fe(CO)4I2、Fe3S2(CO)9、Fe3(CO)12、Fe2S2(CO)6、Cp2Fe2(CO)4和CpFe(CO)2X(Cp=环戊二烯基;X=Cl,I)7种典型的羰基铁化合物。比较系统的阐述了这几种化合物的合成方法以及产物红外光谱的差异,首次发现用Fe(CO)4I2和Na2S快捷合成Fe3S2(CO)9化合物的新方法,并用单晶衍射法证实了该化合物。     

高温煤气化转化CO2为CO

针对CO2难处理、难利用的特点,提出了1种新的CO2资源化利用途径,即将CO2取代水蒸汽作为煤高温气化剂生产CO.通过实验验证了动力学可行性,用ASPEN Plus模拟验证了工艺可行性,并建立了CO2的0排放生产模型和效益分析.     

水合物法分离烟气(CO2/N2)中CO2的实验研究

利用四丁基溴化铵(TBAB)作为促进剂进行了水合物法分离烟气(CO2/N2)的实验研究.结果表明较高TBAB浓度下生成的水合物较多,其中包含更多的未填充气体的纯TBAB水合物;解析气中的CO2含量受到气体消耗率及实验初始压力的影响;TBAB浓度、实验温度在实验条件范围内对解析气中的CO2含量影响并不明显.CO2摩尔分数为17.4%的CO2/N2混合气通过_二级水合物/膜分离流程可回收到CO2摩尔分数为95.0%的解析气.     

基于粉煤气流床气化的CO_2制CO工艺技术研究

利用Aspen Plus软件模拟了以CO2和干煤粉为主要原料的气流床气化生产CO的工艺技术,研究了该工艺路线和反应条件的可操作性和合理性,在此基础上进行了实验室平台实验,实验结果与模拟结果高度吻合,说明采用基于粉煤气流床气化的CO2制CO工艺路线是可行的,进一步分析指出该工艺的两个关键操作指标为温度和压力。研究可为未来放大研究和工艺放大提供理论参考。     

ShiftMax 820的CO转化工艺

采用气化法将烃或煤转化成合成气是个极复杂的课题。许多公开文献及专利均介绍过原料的来源和特性,如煤、重渣油、生物燃料、废气或天然气以及气化工艺、净化步骤、合成气转化工艺以及最终产品。本文讨论将CO转化成合成气,不考虑所用的工艺和碳原料。将不同的CO转化工艺即酸性气变换（SGS）和脱硫气变换工艺加以比较,介绍一种新型酸性气变换催化剂——ShiftMax 820,     

一种褐煤热解煤焦的CO2气化反应特性

针对褐煤的热解-部分气化-残炭燃烧梯级利用工艺,以宁夏石沟驿褐煤为原料,采用水平管式炉在700℃～950℃温度范围内分别制备快速和慢速热解煤焦,考察了煤焦微晶结构和比表面积随制焦条件的变化.利用热重-质谱联用技术研究煤焦CO2气化反应特性,并采用不同评价指标对煤焦气化活性进行了表征.结果表明:气化温度每升高50℃,煤焦CO2气化反应速率增加50％以上;热解温度升高,虽然煤焦微晶结构的有序化程度加深,比表面积减小,但煤焦CO2气化反应活性主要受气化温度影响;快速热解煤焦的CO2气化反应活性高于慢速热解煤焦,二者的差异随着气化温度升高而增大;表征煤焦CO2气化活性的平均比气化速率和反应性指数存在线性关系.     

The metal-chain complexes (X)[Os(CO)3(CNBut)]3Mn(CO)5 (X=Cl,Br, I)

In what is a new metal-chain forming reaction, (X)[Os(CO)₃(CNBu^t)]₃Mn(CO)₅ (X=Cl, Br, I) complexes have been prepared by the successive addition of Os(CO)₄(CNBu^t) to Mn(CO)₅(X) in hexane. The crystal structure of the iodo derivative reveals it to contain an approximately linear Os₃ Mn chain of metal atoms.     

CO/N2/CO2在MOF-74(Ni)上吸附相平衡和选择性

主要研究了MOF-74(Ni)材料对CO/N₂/CO₂的吸附分离性能。应用水热法合成制备MOF-74(Ni),分别采用全自动表面积吸附仪、P-XRD、扫描电子显微镜对材料的孔隙结构和晶体形貌进行了表征,应用静态吸附法测定了CO、N₂和CO₂在MOF-74(Ni)上的吸附等温线,应用DSLF方程模拟了3种气体MOF-74(Ni)上的吸附等温线,依据IAST理论模型计算了MOF-74(Ni)对CO/N₂二元混合物和CO/CO₂二元混合物的吸附选择性。研究结果表明:在0.1 MPa和常温条件下,MOF-74(Ni)材料对CO吸附容量高达6.15 mmol·g^-1,而相同条件下N₂的吸附量只有0.86 mmol·g^-1。MOF-74(Ni)在低压下(0～40 kPa)对CO的吸附量明显高于其对CO₂的吸附量。应用IAST模型估算MOF-74(Ni)对二元混合物吸附选择性的结果表明:MOF-74(Ni)对CO/N₂混合物的吸附选择性在1000以上;MOF-74(Ni)对CO/CO₂的吸附选择性在4～9范围,在所研究的二元气体混合物吸附体系中,MOF-74(Ni)都能优先吸附CO。     

CO oxidation on a Cu(100) catalyst

The oxidation of carbon monoxide by molecular oxygen on a single crystal Cu(100) catalyst was studied at 458 K using reactant gas mixtures with CO/O₂ ratios of 2/1, 10/1 and 25/1 at a total pressure of 10 Torr. The catalytic activities were found to be strongly dependent upon the CO/O₂ ratio. Under stoichiometric reaction conditions (CO/O₂ = 2), the initial CO oxidation activity decreased sharply; with a highly reducing reaction mixture (CO/O₂ = 25), the initial activity gradually increased. These changes in catalytic activities with reactant gas mixture composition correlate with changes in surface composition, namely an increase in the surface oxygen coverage. Post-reaction TPD revealed the presence of a carbonate-like species which decomposed at ca. 630 K.     

Complexes in the Photocatalytic Reaction of CO(2) and H(2)O: Theoretical Studies

Complexes (H(2)O/CO(2), e-(H(2)O/CO(2)) and h(+)-(H(2)O/CO(2))) in the reaction system of CO(2) photoreduction with H(2)O were researched by B3LYP and MP2 methods along with natural bond orbital (NBO) analysis. Geometries of these complexes were optimized and frequencies analysis performed. H(2)O/CO(2) captured photo-induced electron and hole produced e-(H(2)O/CO(2)) and h(+)-(H(2)O/CO(2)), respectively. The results revealed that CO(2) and H(2)O molecules could be activated by the photo-induced electrons and holes, and each of these complexes possessed two isomers. Due to the effect of photo-induced electrons, the bond length of C=O and H-O were lengthened, while H-O bonds were shortened, influenced by holes. The infrared (IR) adsorption frequencies of these complexes were different from that of CO(2) and H(2)O, which might be attributed to the synergistic effect and which could not be captured experimentally.     

Removal of Fe(CO)5 from CO Gas as Detected by FTIR Spectroscopy

FTIR spectroscopy has been used to detect iron pentacarbonyl, Fe(CO)₅, in carbon monoxide gas. The capability of PbO/γ-Al₂O₃ as a compound to remove Fe(CO)₅ in CO gas was investigated using FTIR spectroscopy. The amount of iron pentacarbonyl in the CO gas was determined by spectroscopic means and by a complimentary technique based on the analysis of the iron content of spent PbO/γ-Al₂O₃ particles.     

Elucidation of CO2 Formation Mechanism in CO + NO Reaction on Pd(111) and Pd(110) Surfaces Using IR Chemiluminescence Method

The infrared (IR) chemiluminescence technique was applied to steady-state CO oxidation by NO on Pd(111) and Pd(110). From a comparison of IR emission spectra of CO₂ between the CO + NO and CO + O₂ reactions, it was found that the vibrational energy states of CO₂ in the CO + NO reaction were similar to those in the CO + O₂ reaction. This indicates that the reaction path of CO₂ formation in CO + NO is the same as that in CO + O₂, although the vibrational states are very dependent on the surface structure.     

The Reaction of Allylbenzene and CoH(CO)4

The carbon monoxide uptake in the reaction of allylbenzene with CoH(CO)₄ in n-octane leading to acylcobalt tetracarbonyls and aldehydes is catalyzed by Co₂(CO)₈. The rate is half order in Co₂(CO)₈, first order in allylbenzene and shows a complex dependence in CoH(CO)₄ and CO. From kinetic experiments between 15 and 45° C the temperature dependence of the observed rate constant was determined. The complete analogy of this kinetics with that obtained for heptene-1 shows that the main aldehydic product 2-phenylbutyraldehyde is formed by a mechanism characteristic for aliphatic olefins and not by one operative for styrenes.     

Deactivation of Cu2O(100) by CO Poisoning

We have performed kinetic Monte Carlo (KMC) simulations of 13 reaction processes for CO oxidation on the O-terminated Cu₂O(100) surface to calculate the conversion rate of CO to CO₂. We find that CO adsorption at O vacancy sites prevents dissociative adsorption of O₂ onto the Cu₂O(100) surface and accordingly CO oxidation of the Cu₂O(100) surface is poisoned by CO. As a result, we could obtain a 100 % conversion rate only for a brief period of time.     

Oxidative addition of halogens to MoRu(CO)6(dppm)2

Halogens oxidatively add to MoRu(CO)₆(μ-dppm)₂ (1) at ambient temperature to yield [(CO)₂Mo(μ-X)(μ-CO)(μ-dppm)₂Ru(CO)₂]⁺[Mo(CO)₄X₃]⁻, where X=Cl (2) or I (3), dppm=Ph₂PCH₂PPh₂, and the μ-CO is semi-bridging. Complexes 2 and 3 have been characterized by elemental analysis, conductivity, and NMR spectroscopy, while the molecular structure of 3 has been determined by X-ray crystallography. Ignoring a weak metal–metal bond interaction, the cation of 3 is most easily described as pseudo-octahedral at Ru(II) and Mo(0) centres; the anion is a monocapped octahedron that has been described previously.