污泥与石油焦的共成浆性

采用萘系阴离子表面活性剂作为分散剂,分别考察了剩余污泥和脱水污泥改性前后与石油焦的成浆性。结果表明,加入剩余污泥和脱水污泥可降低水焦浆的成浆质量分数;相同成浆质量分数时,剩余污泥制的污泥焦浆比脱水污泥制的污泥焦浆的表观黏度低;经强碱改性后,两种污泥与石油焦的成浆质量分数均有提高,脱水污泥的成浆质量分数提高更为明显。随着剪切速率的增大,两种污泥焦浆的表观黏度降低,属于假塑性流体。污泥的加入提高了水焦浆的稳定性,起到了稳定剂的作用。     

炼油厂含油污泥与高硫石油焦的共成浆性

利用炼油厂产生的含油污泥和高硫石油焦,采用萘系分散剂制成油泥焦浆。分别考察了含油污泥处理前后与石油焦的成浆性能。结果表明,未经处理的含油污泥可与石油焦共成浆,但成浆浓度远低于石油焦浆;加入硫酸铁后油泥焦浆表观黏度和流动性得到改善,成浆浓度提高;电解质对浆体的降黏效果优于表面活性剂。含油污泥的加入改变了石油焦浆体的流变类型,随着剪切速率增大,油泥焦浆的表观黏度降低,属于假塑性流体;含油污泥的加入提高了石油焦浆体的稳定性,起到了稳定剂的作用。     

造纸黑液对石油焦成浆性的影响

石油焦产量随着原油的劣质化逐年增长,如何有效利用石油焦值得研究。气化技术可以实现石油焦的清洁利用,制浆是石油焦气化至关重要的一步。考察了造纸黑液对石油焦成浆性的影响。结果表明,在石油焦质量分数为65%时,石油焦不能单独成浆。造纸黑液能够极大地改善石油焦的成浆性。随着造纸黑液添加量的增大,石油焦的成浆黏度先减小后增大,当造纸黑液添加量为石油焦质量的1%、剪切速率为100s-1时,石油焦浆黏度出现最小值520mPa s。造纸黑液添加量存在最高限度,即为石油焦质量的5%。在造纸黑液的最优添加量下,石油焦的最高成浆质量分数为70%。造纸黑液添加量在0.6%~10%、石油焦质量分数为65%时,水焦浆在2d内均不产生不可恢复的硬沉淀,能满足气化生产要求。     

芥酸酰胺丙基二甲基叔胺改性纤维素溶液的 流变性能与交联性能

为了改善纤维素溶液的增稠能力和交联性能,合成了一种新型疏水醚化改性剂(3-氯-2-羟丙基芥酸酰胺醋酸铵),并采用该改性剂对羧甲基羟乙基纤维素(CMHEC)进行疏水改性,首次制得了芥酸酰胺丙基二甲基叔胺疏水改性纤维素(ED-CMHEC),研究了CMHEC和ED-CMHEC溶液的流变性能(表观黏度、流动曲线、触变性和黏弹性)和交联性能。研究结果表明,改性后ED-CMHEC溶液的表观黏度得到显著提升并表现出更显著的触变性与黏弹性。质量分数0.3%的CMHEC和ED-CMHEC溶液在30℃、170 s~(-1)的表观黏度分别为18 mPa·s和71mPa·s,后者较前者提高了2.94倍。不同质量分数(0.3%数0.5%)的CMHEC和ED-CMHEC溶液均表现出剪切变稀性质,其流动曲线可用Cross模型进行描述。有机锆交联剂FAC-201加量为0.2%时,质量分数0.3%ED-CMHEC溶液交联形成凝胶的黏度是改性前的2.4倍,表现出更强的交联性能。图9表4参22     

炼油厂含油污泥离心脱水技术的探索

对含油污泥进行了组成的剖析和微观研究，通过絮凝剂筛选和添加助剂粉焦对含油污泥进行调质改性，在实验室和工业试验中取得了含油污泥水固两相离心分离的满意效果。当含油污泥密度大于1.0008g/cm^3。含油小于3%时，加入200μg/gCPAM-邕凝剂调质，可以顺利进行离心脱水，当密度略小于1g/cm^3时，加入1.5%粉焦调质，可以明显改善离心脱水效果，使离心液的COD质量浓度达到标准，该技术应用后，不仅解决了目前炼油行业普遍存在的含油污泥脱水难题，还有一定的经济效益。     

纳米改性CMC的制备、结构表征和性能评价

选用锌类纳米材料ZZ作为纳米复合处理剂的制备原料，采用溶液共混法与乳液共混法为主、机械共混法为辅的共混方法制得了纳米改性材料CMC-ZZ。红外光谱谱图测试结果表明，CMC与ZZ表面通过氢键结合形成吸附层；应用扫描电镜对纳米改性材料进行结构分析表明，纳米材料ZZ与CMC并非简单地混合在一起，而是发生了物理／化学作用；性能评价结果表明，纳米改性材料CMC-ZZ能改善钻井液的护胶性能，降低常温及高温高压滤失量，同时也能提高塑性黏度和动切力，所以CMC-ZZ能明显提高钻井液老化后的表观黏度。因此当需要提高钻井液高温（大于180℃）下的动切力时，可选用纳米改性材料CMC-ZZ。     

超临界CO_2中疏水改性聚丙烯酸的合成及其溶液性质

在水溶性单体丙烯酸(AA)与疏水性单体丙烯酸十八酯(ODA)中,加入N,N′-亚甲基双丙烯酰胺(MBAM),在超临界CO_2介质中合成了疏水改性聚丙烯酸(HMPAA)。采用扫描电子显微镜、乌氏黏度计和旋转黏度计对HMPAA的性质进行了表征,考察了温度、HMPAA溶液质量浓度、MBAM含量、HMPAA溶液pH对HMPAA溶液表观剪切黏度的影响。实验结果表明,HMPAA为白色粉末,由粒径约2μm的颗粒组成;HMPAA溶液表观剪切黏度随HMPAA溶液pH的增大先增大后降低;HMAA溶液表观剪切黏度随HMPAA溶液质量浓度的增加而增大;当MBAM的质量分数小于0.51%时,HMPAA溶液表观剪切黏度随MBAM含量的增加而增大。当HMPAA溶液质量浓度为0.8 g/dL、温度30℃、m(AA):m(ODA)=9:1、w(MBAM)=0.51%时,HMPAA溶液的表观剪切黏度达到75.0Pa·s。     

碱与乳化剂复合体系对稠油乳状液稳定性及流变性的影响

考察了Na2CO3、非离子型乳化剂BJN-01、无机盐加量对水包稠油型乳状液分水率和表观黏度的影响,分析了复合体系对乳状液稳定性和流变性的作用规律及协同作用机理。结果表明,碱质量浓度为500 mg/L、乳化剂体积分数为0.5%时形成的乳状液最稳定,室温静置19 h的分水率为60.7%,且表观黏度较低,30℃与20.4 s-1下的表观黏度为86.2 m Pa·s;加入Na Cl使乳状液的稳定性降低,且盐浓度越高、分水率越大;当乳化剂体积分数为0.5%,碱加量在500~6000 mg/L时,随着碱浓度增加,乳状液的稳定性降低,表观黏度增加;当碱加量为500 mg/L,乳化剂体积分数在0.5%~0.9%时,随着乳化剂加量增大,乳状液的稳定性增强,表观黏度增加。     

有机碱和无机碱对原油的乳化性质及对聚合物黏度的影响

以乙二胺作为有机碱,NaOH作为无机碱,利用乳化实验和黏度测量实验,对两种碱与稠油的乳化行为及两种碱对聚合物黏度的影响进行了研究。结果表明,乙二胺的加入基本不增加溶液矿化度,其质量分数的增加不会促使油包水乳状液的形成,且在NaCl质量分数不大于1.2%时,0.2%~1.0%的乙二胺可将稠油乳化成较稳定的水包油乳状液;而NaOH的加入会增加溶液的矿化度,即使溶液中不加NaCl,0.6%以上的NaOH会促使油包水乳状液的形成,不利于水包油乳状液的稳定,且不同NaCl质量分数下1%的NaOH溶液都会把稠油乳化成油包水乳状液。溶液中NaOH的加入会大大降低聚合物的黏度,当NaOH质量分数为1%时,聚合物的黏度会降低一半多;而乙二胺的加入基本不增加溶液矿化度,不仅不会降低聚合物黏度,反而可以使聚合物的黏度有所上升。由此可知,乙二胺在原油开采及提高原油采收率方面相对NaOH有较大优势。     

碱、表面活性剂对新疆稠油乳状液稳定性及流变性的影响

研究了Na_2CO_3、甜菜碱表面活性剂、NaCl加量对水包油型乳状液稳定性和表观黏度的影响,利用TURBISCAN LAB稳定分析仪,哈克流变仪采用控制变量法分析了碱、表面活性剂、盐含量对乳状液稳定性和流变性的影响机理。结果表明,在活性剂体积分数为0.3%的条件下,Na_2CO_3质量浓度为500mg/L时形成的乳状液最稳定,稳定分析仪扫描1h试样平均背散射光强值变化值约为2.17%,且体系表观黏度较低,40℃下为96.3mPa·s,碱加量在500~4 000mg/L时,随着Na_2CO_3质量浓度增加,乳状液的稳定性降低,体系表观黏度增加;在Na_2CO_3质量浓度为500mg/L的条件下,随着表活性剂体积分数的增大,体系稳定性增强,当活性剂体积分数为0.3%时,体系表观黏度最低,40℃下为98.2mPa·s,活性剂体积分数在0.3%~0.7%时,随着活性剂体积分数增大,乳状液的稳定性增强,体系表观黏度增加;加入NaCl使乳状液的稳定性降低,且NaCl质量浓度越高、稳定性越差。     

Analysis of petroleum coke from low grade oily sludge of refinery

Petroleum coke is often shortened as pet coke. Petroleum coke or pet coke is a product obtained from oil of all kinds during the oil refining process. Petroleum coke is a carbon-rich solid originating from petroleum refining and is obtained by cracking process. Petroleum coke is a byproduct of the coking unit, a residual fuel upgrader. The coke quality depends on the crude oil processed in refinery. The mixture of oil, solids and water deposited at the bottom of the storage deposit is known as waste oil sludge. Oil sludge is one of the solid wastes produced in petroleum refinery and it is a complex emulsion composed of various petroleum hydrocarbons, heavy metals, solid particles, and water. As a result of the refining process of crude oil, the contaminated sludge is biodegraded and converted into waste products that damage the environment and human health. In the coke processing, the assessment of oil sludge fraction is based on the principle of heating to high temperatures and the removal of light fractions from the breakdown. If the oil sludge initially contains low levels of sulfur and metal, the resulting petroleum coke is then calcined before use. The high quality needle type coke produced on convenient conditions in the coking unit.     

Improved Purification of Petroleum Coke for Grease Lubricants by a Flotation Process

The surface and thermodynamic properties of the anionic surfactant were studied together with its efficiency on being used as a collector in the flotation of petroleum coke. The surface tension of the aqueous solution was measured at 25°C and the surface excess concentration as well as the critical micelle concentration of the mixtures were investigated. There was a good relationship between the adsorption effectiveness of the phase transfer catalyst (cationic) and the efficiency of the collector. A synergistic effect was observed for the phase transfer catalyst and the anionic collector reducing the surface tension of the aqueous solution in the purification of petroleum coke. The results showed the best mole fraction of mixture (anionic/ cationic)which is preferable to be used as the flotation collector. The optimum conditions for purification of petroleum coke were determined so as to acceptably use this coke for the lubricating grease.     

改变操作方式降低石油焦中挥发分含量

石油焦既是水泥、玻璃、电厂等行业的燃料,也是铝用碳素等行业不可或缺的原材料,焦化是唯一能生产石油焦的工艺过程。长期以来,中国石油乌鲁木齐石化公司1.20×10~6 t/a延迟焦化装置生产的石油焦仅能达到3A、3B及以下等级技术要求,利润率低下。分析发现,挥发分含量高是制约石油焦质量提升的关键因素。结合企业生产实际情况,在不增加设备投入的前提下,提出提高焦炭塔入口温度、降低"三泥"回炼量、增大焦炭塔大吹汽量等措施。结果表明,该方案切实、可靠、可行,可将石油焦中挥发分质量分数降至12%以下,达到2A级质量标准,并使全厂2A、2B石油焦产量占比提高58%,以较低成本实现了石油焦产品的差异化发展路径。     

石油焦作为粉煤气化原料的可行性分析

为了验证石油焦作为粉煤气化原料的可行性，对其基本性质、疏水性、挥发性和流动性进行了分析，并与3种典型的煤进行了对比。结果表明:石油焦性质与晋城无烟煤最为相近，具有热量高、含碳质量分数高的特点；石油焦中主要包含芳香烃、烷烃、双键烃基等疏水基团，不易与水互溶；石油焦粉在制粉干燥过程中无挥发性有机物析出，不易吸湿结团，能够满足粉煤气化制粉单元的需求；石油焦粉的流动性优于煤粉，在加压输送单元不易发生架桥现象。     

Improved Purification of Petroleum Coke for Grease Lubricants by a Flotation Process

Abstract

The surface and thermodynamic properties of the anionic surfactant were studied together with its efficiency on being used as a collector in the flotation of petroleum coke. The surface tension of the aqueous solution was measured at 25°C and the surface excess concentration as well as the critical micelle concentration of the mixtures were investigated. There was a good relationship between the adsorption effectiveness of the phase transfer catalyst (cationic) and the efficiency of the collector. A synergistic effect was observed for the phase transfer catalyst and the anionic collector reducing the surface tension of the aqueous solution in the purification of petroleum coke. The results showed the best mole fraction of mixture (anionic/ cationic)which is preferable to be used as the flotation collector. The optimum conditions for purification of petroleum coke were determined so as to acceptably use this coke for the lubricating grease.     

The Leaching Behavior of Toxic Metals in Petroleum Sludge After Thermal Treatment

Petroleum sludge contains high concentration of hydrocarbons and heavy metals, which are hazardous to the environment and human health. In this study typical petroleum sludge samples collected from crude oil tank were thermal treated by burning and melting, respectively. The leaching behavior of seven target heavy metals including Cr, Ni, Cu, Zn, As, Cd, and Pb from the solid residue were comparatively studied with that from municipal sewage sludge according to the toxicity characteristic leaching procedure. Scanning electron microscopy and X-ray diffraction analysis were carried out to investigate the morphology and crystalline composition. Results showed that total concentrations of target metals in petroleum sludge were relatively lower comparing with those in sewage sludge except for Cu, Cd, and Pb. Leached concentrations of Cu, As, and Pb from petroleum sludge increased dramatically after burning and were higher than those from sewage sludge. The leached concentrations after melting were decreased substantially except for Cr and Ni whose leaching concentrations were unaffected by thermal treatment for the studied samples.     

流化床中造纸黑液催化石油焦气化特性

利用实验室规模流化床气化反应器,考察了造纸黑液对石油焦水蒸气气化反应的催化效果,并分析了其催化反应机理。结果表明,造纸黑液不仅能显著提高石油焦的气化反应活性,还能大幅提高气化气中H₂的含量。脱水黑液添加量为黑液与石油焦质量之和的10%时催化效果较好,达到相同气化反应速率时的反应温度比纯石油焦气化低200℃左右;在相同反应温度下提高气化反应速率5倍左右,可提高气化气中H₂体积分数约8百分点。黑液中的碱金属活性组分能够破坏石油焦中的C=C芳香结构,同时与石油焦中的碳结合生成活性较高的碳氧复合物C(O),从而提高气化反应速率;碱金属还促进了水煤气变换和CH₄水蒸气重整反应,使得H₂的生成量增多。因此,造纸黑液是一种有效的石油焦气化生产富氢合成气的催化剂。     

Preparation and properties of oil-substituted fuel based on petroleum coke with biomass fermentation

To improve the stability of petroleum coke water slurry (PCWS), bubble-PCWS based on biomass fermentation was researched in this paper. The results showed that the stability of bubble-PCWS improved as biomass dosage increased. The bubble-PCWS with yeast could reach a high solid concentration of 65?wt% and a perfect stability with water segregation rate being 0?wt% and pour out rate being more than 90?wt%, when the straw dosage was 3?wt%. The bubble-PCWS with activated sludge possessed good recoverability, but the solid concentration and the pour out rate obviously decreased as the sludge increased.     

含油污泥高温好氧发酵研究

探讨了含油污泥高温好氧发酵的可行性,研究了不同发酵方式、外加营养成分以及回用发酵腐熟料对污泥稳定化和无害化的影响程度。结果表明：脱水含油污泥添加鸡粪等营养成分后可实现快速发酵升温和稳定化,油类去除率可达60%左右;采用厌氧与好氧联合发酵的方式时油类的降解率并不比直接好氧发酵法高;发酵腐熟料可直接回用作为含油污泥好氧发酵的部分调节剂和膨松剂。含油污泥高温好氧发酵的建议参数为：反应仓的通风量控制在0.025～0.050 m3/(m3?h),含油污泥与鸡粪等禽畜粪便的体积比为3:1。