Preparation of p-Hydroxybenzaldehyde by Hydrolysis of Diazonium Salts Using Rotating Packed Bed

A new type of reactor,featured with impinging stream-rotating packed bed（IS-RPB）and coil pipes,was designed and used to prepare p-hydroxybenzaldehyde（PHB）by hydrolysis from diazonium salts.The influence of operating parameters,such as reaction temperature,reaction time and high gravity factor,on the yield of PHB was investigated.Compared with the traditional kettle-type reactor,the yield of PHB with the new reactor is increased significantly and the reaction time is much shorter.Under the optimum conditions,the yield of PHB is increased from 51%to 84.1%.The reactor offers an opportunity for replacing the traditional batch mode operation with a continuous process.

Influence of Salt Beds on the Segmentation of Structure and Hydrocarbon Accumulation in Qiulitag Structural Belt,Tarim Basin,China

Seismic information and balanced profile technology were used to reveal the influence of the salt bed in segmentation of structure and hydrocarbon accumulation in Qiulitag structural belt in Tarim basin. From west to east, the shortening of strata above the salt beds gradually decreases, while, the shortening below the salt beds gradually increases, which shows that the segmentation of structure integrated the seismic profile. There is great difference of the deformation of strata below and above the salt beds between the west segment and the east segment. The analysis of the distribution of oil/gas fields and the hydrocarbon properties indicates the similar segmentation to the structure segmentation. The salt beds in relatively shallow layers change the stress condition from basement of Kuqa foreland basin, which leads to the segmentation of Qiulitag structural belt. Because the salt beds in the west segment came into being earlier than those in the east segment, the west segment captures hydrocarbon from two sets of source rock, while the east segment can only capture hydrocarbons from one set of source rock. So, the salt beds play an important role in the segmentation of structure and hydrocarbon accumulation.

Mathematical modeling of salt-gradient ion-exchange simulated moving bed chromatography for protein separations

The salt-gradient operation mode used in ion-exchange simulated moving bed chromatography (SMBC) can improve the efficiency of protein separations. A detailed model that takes into account any kind of adsorption/ion-exchange equilibrium, salt gradient, size exclusion, mass transfer resistance, and port periodic switching mechanism, was developed to simulate the complex dynamics. The model predictions were verified by the experimental data on upward and downward gradients for protein separations reported in the literature. All design and operating parameters (number, configuration, length and diameter of columns, particle size, switching period, flow rates of feed, raffinate, desorbent and extract, protein concentrations in feed, different salt concentrations in desorbent and feed) can be chosen correctly by numerical simulation. This model can facilitate the design, operation, optimization, control and scale-up of salt-gradient ion-exchange SMBC for protein separations.

Study on neutronics design of ordered-pebble-bed fluoride-salt- cooled high-temperature experimental reactor

This paper presents a neutronics design of a 10 MW ordered-pebble-bed fluoride-salt-cooled high-temperature experimental reactor. Through delicate layout, a core with ordered arranged pebble bed can be formed,which can keep core stability and meet the space requirements for thermal hydraulics and neutronics measurements.Overall, objectives of the core include inherent safety and sufficient excess reactivity providing 120 effective full power days for experiments. Considering the requirements above, the reactive control system is designed to consist of 16 control rods distributed in the graphite reflector. Combining the large control rods worth about 18000–20000 pcm, molten salt drain supplementary means(-6980 to -3651 pcm) and negative temperature coefficient(-6.32 to -3.80 pcm/K) feedback of the whole core, the reactor can realize sufficient shutdown margin and safety under steady state. Besides, some main physical properties, such as reactivity control, neutron spectrum and flux, power density distribution, and reactivity coefficient,have been calculated and analyzed in this study. In addition, some special problems in molten salt coolant are also considered, including ~6Li depletion and tritium production.

Experiments on mechanical properties of salt rocks under cyclic loading

The primary purpose of underground gas storages is to provide gas for seasonal consumptions or strategic reserve.The periodical operations of gas injection and extraction lead to cyclic loading on the walls and surrounding rocks of gas storages.To investigate the mechanical behaviors of different host rocks in bedded salt deposit,laboratory experiments were conducted on the samples of rock salt,thenardite,glauberite and gypsum.The mechanical properties of rock samples under monotonic and cyclic loadings were studied.Testing results show that,under monotonic loading,the uniaxial compressive stress（UCS） of glauberite is the largest（17.3 MPa）,while that of rock salt is the smallest（14.0 MPa）.The UCSs of thenardite and gypsum are 16.3 and 14.6 MPa,respectively.The maximum strain at the peak strength of rock salt（halite） is much greater than those of the other three rocks.The elastic moduli of halite,thenardite,glauberite and gypsum are 3.0,4.2,5.1 and 6.8 GPa,respectively.Under cyclic loading,the peak strengths of the rock specimens are deteriorated except for rock salt.The peak strengths of thenardite,glauberite and gypsum decrease by 33.7%,19.1% and 35.5%,respectively;and the strains of the three rocks at the peak strengths are almost the same.However,the strain of rock salt at the peak strength increases by 1.98%,twice more than that under monotonic loading.Under monotonic loading,deformation of the tested rock salt,thenardite and glauberite shows in an elastoplastic style.However,it changes to a ductile style under cyclic loading.Brittle deformation and failure are only observed for gypsum.The results should be helpful for engineering design and operation of gas storage in bedded salt deposit.

Statistical evaluation of five failure criteria for intact salt rock

Five multiparameter empirical criteria were exclusively evaluated by comparing them with the strength data covering various stress conditions to find out which failure criterion best fits the test data and describes the mechanical behavior of the salt rock sequence (halite,bedded composite specimens and anhydrite interlayers).Full-scale comparison of all criteria for the three rock types was conducted based on five standard statistics calculated from least squares curve-fitting,which measures both the goodness of fitting and the quality of future prediction.The results indicate that all five nonlinear criteria with a basic power form are efficient in predicting the strength trend in the low tension area as well as in the high compression area of the soft rocks.The parameters obtained for the bedded rock salt are somewhat in the ones for the "pure" rocks and are even closer to those obtained for the halite.The generalized Hoek-Brown criterion is proven to perform best to two rock strength data followed by one for the Bieniawski empirical criterion,thus is the best candidate for the analysis of the salt rock.The Sheorey empirical criterion consistently achieves an intermediate performance for all the three rocks.It seems that the superiority of the poly-axial criteria (the Mogi 1967 criterion and the N-type criterion) over the former three triaxial criteria no longer exists when applied to the conventional triaxial strength data.Besides,the method of tension cut-off was proposed to solve the ambiguity problem of the two poly-axial criteria in the tension field in the plane of the major (σ1) andminor principal stress (σ3).

中国大规模盐穴储氢需求与挑战

氢能是来源广泛且低碳清洁的能源,大力发展氢能产业是实现双碳目标和应对全球能源转型的重要举措。在氢能“制备―储存―运输―应用”全产业链中,储氢难问题长期制约着氢能产业高质量发展。盐穴储氢具有成本低、规模大、安全性高和储氢纯度高等突出优势,是未来氢能大规模储备的重要发展方向,也是我国能源低碳转型的重大战略需求。综合调研了我国制氢产业和氢能消费现状,分析了我国盐穴储氢的需求。调研了国外利用盐穴储存天然气和氢气的技术及工程现状,总结了我国盐穴储气库发展和建设历程。对比了利用盐穴储存天然气、氦气、压缩空气和氢气的异同点,提出我国盐穴储氢面临三大科技挑战:层状盐岩氢气渗透与生化反应、盐穴储氢库井筒完整性管控、储氢库群灾变孕育与防控。研究成果明确了我国氢气储备需求的快速增长趋势和大规模盐穴储氢的重点攻关方向。

Roles of gypsum/salt-bearing sequence in hydrocarbon accumulation and storage

Gypsum/salt beds are widely developed in petroliferous basins across the world.Most basins with gypsum/salt beds have been proven to host abundant hydrocarbon resources.Previous studies on the effects of gypsum/salt beds on hydrocarbon reservoirs primarily focused on their excellent sealing property as cap rocks.However,an increasing number of exploration discoveries have shown that gypsum/salt beds have the potential to promote the formation of high-quality source rocks and hydrocarbon reservoirs.Gypsum/salt beds influence the generation,preservation and accumulation of hydrocarbons.Based on the systematic analysis of the generation of hydrocarbons in global gypsum/saltbearing sequences,the study discussed the control of gypsum/salt beds on play elements,and explore the relationship between the development of gypsum/salt beds and global large-and medium-scale hydrocarbon reservoirs.Furthermore,we analyzed the correlation between typical gypsum/saltbearing sequences and their hydrocarbon generation potentials in China.In-depth analysis shows three patterns in terms of the spatial superimposition of gypsum/salt beds and source rocks,that is,postsalt pattern,inter-salt pattern and pre-salt pattern.Among others,the source rocks of the inter-salt pattern are widely developed in salt basins and of great potential for hydrocarbon exploration.

基于圆柱封装单元的水合盐相变储热填充床的储释特性实验研究

水合盐相变储热技术具有储热密度高、成本低等优势,在清洁供暖中具有广阔应用前景。本研究设计并搭建了以三水合乙酸钠作为储热材料,以圆柱形相变材料封装单元作为基础单元的填充床相变储热装置。通过实验研究填充床储热装置的运行特性,研究了流量和储热温度对装置的储释热用时、出口温度、热效率及储热密度的影响。实验结果表明:提高储热温度和增大流量可缩短储热用时、提升热效率和储热密度。储热装置的热效率可达94.73%,储能密度可达71.77 kW·h/m^(3)。

鄂尔多斯盆地中东部奥陶系盐下层系白云岩储层沉积特征及发育演化机理

鄂尔多斯盆地马家沟组盐下的碳酸盐岩—蒸发岩层系是未来油气勘探的重要接替层系。由于碳酸盐岩—蒸发岩的特殊沉积组合强烈影响后续差异化成岩流体溶蚀—充填作用,进一步增大了盐下碳酸盐岩储层的复杂性,也给优质储层的分布预测增加了难度。本文以鄂尔多斯盆地马家沟组中下组合为研究对象,基于岩心、薄片、物性资料等开展储层地质学研究,识别出15种岩石类型和10类相序组合,明确了盐下储层类型包括:膏模孔泥晶云岩储层、颗粒白云岩储层、斑状白云岩储层、晶粒白云岩储层和微生物白云岩储层。在孔隙成因和演化分析基础上,建立了“优势沉积相+早期成孔+膏盐岩封盖保存孔隙”的盐下白云岩储层发育地质模式。研究结果深化了对盐下碳酸盐岩层系孔隙形成和保存机理的认识,同时对鄂尔多斯盆地的油气资源勘探开发具有重要的现实意义。

一种具有“盐响应”特性的两性离子聚合物增黏降滤失剂

随着深层、超深层及非常规油气开采的不断深入,钻井过程中盐污染已成为水基钻井液在极端盐度和高温条件下面临的严峻挑战,盐污染会导致钻井液流变性和滤失性能的急速恶化。为避免上述问题发生,通过自由基聚合反应研发了一种具有“盐响应”特性的两性离子聚合物增黏降滤失剂(PAMN),并利用红外光谱分析(FT-IR)、核磁共振氢谱分析(1H-NMR)、热重分析(TGA)、分子模拟技术(MS)、扫描电镜(SEM)及钻井液流变和滤失分析等实验方法,表征了PAMN的分子结构、热稳定性及增黏降滤失性能,并揭示了PAMN的“盐响应”机理。研究结果表明:①合成的PAMN热降解温度高达285℃,PAMN分子链在饱和盐水中的均方位移、扩散系数及回转半径远大于其在纯水中,其回转半径分别为12.5Å和3.8Å;②当氯化钠含量为0时,PAMN分子链内或分子链间正负离子基团通过静电吸引力形成空间网络形态而卷曲成类球状结构,随着氯化钠含量增加,其分子链逐渐转变为溶解性更好的柔性链状结构,对氯化钠表现出正响应性;③PAMN可将饱和盐水钻井液表观黏度增加542.9%,滤失量从194 mL降低至4.8 mL,具有良好的增黏和降滤失性能。结论认为,PAMN的研发成功从根本上实现了传统钻井液处理剂从“抗盐”到“盐响应”的转变,该产品在含盐膏的深层、超深层油气开发工程中具有广阔的应用前景。

生物质合成灰的烧结熔融特性和矿物转变规律实验研究

【目的】研究生物质在流化床燃烧过程的结焦问题,分析钾盐形式和含量对生物质灰烧结熔融特性的影响。【方法】借助扫描电子显微镜耦合能谱仪、X射线衍射仪、X射线荧光分析仪和FactSage热力学计算软件,通过实验分析了生物质合成灰的烧结熔融特性和矿物转变规律。【结果】在流化床的典型运行温度750~950℃范围内,合成灰的烧结熔融程度随温度以及钾盐质量分数的增加而加剧。此外,钾盐形式不同,其对生物质合成灰的烧结熔融特性的影响也有显著差异:钾盐为K_(2)CO_(3)时,合成灰中液相比例最高可达34.36%,合成灰由此发生严重烧结;钾盐为KCl时,大部分K和Cl元素在750~850℃逃逸,合成灰的烧结程度较K_(2)CO_(3)有所减弱;钾盐为K2SO4时,合成灰中液相含量最少,烧结熔融程度也最弱。【结论】改变钾盐的存在形式并控制床温,有望缓解生物质在流化床燃烧过程的结焦问题。

熔盐改性氧化镁吸附剂制备及固定床低浓度CO_(2)吸附捕集

针对吸附法捕集烟道气CO_(2)成本和能耗较高问题,研究采用六水氯化镁和碳酸氢钠通过沉淀法制备碱式碳酸镁并煅烧制得氧化镁粉体,再通过硝酸钠和碳酸钠浸渍改性并成型为(Na NO_(3))_(0.1)-Mg O和(Na NO_(3))_(0.1)(Na_(2)CO_(3))_(0.05)-Mg O颗粒状吸附剂。采用X射线衍射等表征手段对两种吸附剂颗粒微观结构进行分析,并结合热重实验评估了CO_(2)吸附/解吸动力学和循环稳定性。进行了硝酸钠/碳酸钠改性氧化镁吸附剂颗粒填充床低浓度CO_(2)气体的吸附解吸实验研究,分析了氧化镁表面负载的硝酸盐和碳酸盐对低浓度CO_(2)条件下捕集的强化作用。结果表明,在300℃左右,硝酸钠能够在氧化镁表面形成熔盐层,显著强化了CO_(2)吸附性能;硝酸钠熔盐层内存在CO_(2)扩散阻力,需要一定的CO_(2)分压作为通过熔盐层所需的传质推动力,进而降低了低浓度CO_(2)吸附量;碳酸钠的添加可降低CO_(2)通过熔盐层所需的传质推动力,提高低浓度CO_(2)吸附量。

下川东震旦系气井复杂处理技术实践与认识——以YT1井为例

为了安全有效开发四川盆地下川东地区震旦系气藏,保障川渝地区天然气能源的有效接替,需对震旦系气井的开发难点进行研究,解决易发生的故障复杂。以中国石油西南油气田公司重点探井YT1井为研究对象,分析了该井面临的地层多压力系统、压力系统窗口大、井漏严重、井壁易缩径等地质难点,从井身结构、堵漏技术、防溢流技术、防塌技术等方面开展复杂处理技术研究。研究结果表明:①优化井身结构为五开非标结构,能有效封隔必封点;②大井眼段下侏罗统自流井组—上二叠统龙潭组综合应用随钻堵漏、复合堵漏、水泥堵漏技术,可有效提升堵漏成功率,降低复杂时率;③241.3 mm井眼奥陶系十字铺组—上寒武统洗象池组优化钻具组合,综合治理溢、漏、塌等复杂,可有效提升作业效率。结论认为:①沙溪庙—凉高山地层采用空气/雾化钻进未发生故障复杂,防漏、提速效果显著;②龙潭组—下寒武统筇竹寺组地层优选“水力振荡器+复合钻头+MWD定向”技术,23趟钻完成3150.94 m长段膏盐层井段定向作业;③190 mm井眼开展185 mm双向微扩眼器试验,解决了长段膏盐层缩径问题,三次扩眼后下套管顺利到位;④通过复杂防控技术集成应用,YT1井复杂时率降低至17.47%,避免了恶性卡钻;⑤推广应用下川东地区震旦系气藏复杂防控技术对川渝地区后续震旦系气藏深井技术研究具有指导意义。

除盐水再生废水回用促进PTA废水厌氧污泥颗粒化工业实践

福建福海创石油化工有限公司将含有高浓度无机盐的除盐水再生废水引至精对苯二甲酸(PTA)厂区废水处理装置,把高浓度的无机盐均匀稀释,补充至PTA废水上流式厌氧污泥床(UASB)厌氧反应器,作为厌氧微生物微量元素营养剂添加。装置运行4个月后,颗粒污泥占厌氧污泥总量的60%以上,厌氧反应器化学需氧量(COD)降低率提升5百分点以上,说明除盐水再生废水对厌氧污泥颗粒化有明显促进作用。

活性炭吸附工艺在工业废盐综合利用中的性能实验研究

利用固定床和吸附池实验研究了活性炭对盐溶液总有机碳(TOC)的吸附作用,结果显示:浸泡处理后的活性炭在固定床反应器运行初期的吸附能力要优于未处理,但在运行中后期两者差异减小;随着有机负荷的增大,固定床中活性炭的吸附容量利用率提高;相比于降流式,升流式固定床中活性炭吸附容量更高,出水有机物相对浓度更低;粉末状活性炭在吸附池反应器中的有机物脱除效果要好于颗粒状。吸附池的活性炭投加量要远小于固定床,且利用率更高,水处理起效更快,固定床吸附容量小,活性损失慢。

盐膏层双级固井设计方法及施工措施应用

双级固井在钻井的固井工艺中是比较常见的固井工艺。然而双级固井应用在盐膏层地层中又有很多的困难和难点。为此,重点研究了盐膏层双级固井的设计方法并在实践中总结出了较为成功的施工措施,旨在为相关领域的专业人士提供参考和借鉴。

偶氮二氰基戊酸副产废盐热处理工艺研究

以偶氮二氰基戊酸副产废盐为原料,使用管式炉模拟固定床热处理废盐,考查不同热处理温度、反应时间对废盐中TOC含量的影响。实验结果表明,当热处理温度700℃、停留时间为20 min时,废盐中的总有机碳(TOC)含量降至25 mg/kg,白度达到83.46,满足工业用盐质量标准,该研究为废盐资源化利用以及降低企业危废处理成本提供参考。

济阳坳陷东营凹陷古近系红层—膏盐层沉积特征及模式

济阳坳陷东营凹陷古近系孔店组一段—沙河街组四段下亚段(Ek1-Es4x)沉积时期发育了规模巨大的红层—膏盐层沉积。通过对红层—膏盐层沉积构造、碎屑颗粒粒度和沉积物垂向叠加样式等分析,表明红层沉积具有水上沉积作用和水下沉积作用共存、重力流沉积作用与牵引流沉积作用并存的特征。红层—膏盐层在盆地的不同位置具有明显不同的垂向叠加样式。通过地球化学特征分析和泥岩颜色分析,结合前人研究表明,红层—膏盐层沉积时期沉积环境以干旱为主,呈现干湿频繁交替的特征。气候相对潮湿时期,湖盆盐度较低,以沉积砂泥岩为主;气候干旱时期,湖盆盐度高,以沉积膏盐岩为主。红层—膏盐层沉积早中期为低水位振荡性湖泊,沉积晚期为高水位振荡性湖泊,两者沉积作用存在较为明显的差别。

盐穴储气库溶腔收缩规律分析

盐穴储气库在运行过程中溶腔周围的盐层受到地层压力和溶腔内压的多重作用而产生应力变化。由于盐层具有蠕变特性,并且溶腔内压力始终小于周围岩层的地层压力,因此溶腔周围盐层会产生指向溶腔内部的位移而导致溶腔收缩,从而引发储气库单腔库容和工作气量的变化。溶腔的收缩可以通过盐层蠕变测试结合数值模拟进行预测。通过对国内某盐穴储气库实际岩石力学参数测定和溶腔运行模拟预测发现,溶腔建成初期有一个短暂的快速收敛阶段,后期收敛速度较为平稳并有逐步减缓的趋势。运行10年,溶腔的体积缩小逾8%,对应的储气库库容和工作气量也将减少8%以上。因此在盐穴储气库运行的初期,必须密切注意溶腔蠕变,制定合理的运行参数,确保溶腔快速收缩阶段的溶腔稳定。在中后期必须新建溶腔,以弥补因溶腔收缩而减少的库容量及工作气量。