我国煤化工发展现状及前景

煤炭的综合利用与深加工对于以煤炭为主要能源的国家来说至关重要,这不仅提高了煤炭利用率,提高了煤炭的经济效益,而且也有利于环保。因此,煤化工产业的发展近年来取得了较快发展。笔者综述了我国煤化工发展现状及前景,主要包括煤气化、煤液化、煤制烯烃及煤制天然气领域,呼吁加强煤化工企业的自主创新能力,促进煤化工产业的稳步发展。     

我国煤化工标准现状及展望

我国煤炭资源丰富,煤化工技术是重要的能源战略需求之一。我国现已形成以煤焦化、合成氨等为主的传统煤化工产业和以煤气化、煤液化为核心的煤制天然气、煤制油、煤制烯烃、煤制芳烃等现代煤化工产业。完善的煤化工标准化体系有利于行业进一步发展,因此本文全面综述了煤化工标准化工作的研究情况,统计了我国煤化工领域现行和即将实施的国家及行业标准,重点从煤气化、煤间接液化、煤直接液化、煤制天然气、煤制甲醇、煤制烯烃、煤制芳烃、煤制乙二醇、煤制二甲醚等9个主要领域介绍了现代煤化工标准的制定情况并对新标准的制定提出建议。我国煤化工标准体系由基础标准、管理标准、产品标准和检验检测标准4大类构成。截至2019年1月,据不完全统计,我国煤化工领域已颁布实施国标、行标229项,其中,基础标准5项;传统煤化工领域标准154项,2019年1月后实施标准3项;现代煤化工领域标准70项,2019年1月后实施标准12项。传统煤化工标准类别覆盖较为全面,但应加快标准的修订更新工作以加速淘汰落后技术,助力化解产能过剩;现代煤化工标准工作虽然近年来有了长足的进展,但主要问题在于已颁布实施的标准多偏重检验检测方法类,而煤基产品类标准偏少且仅覆盖产业链少数主要产品,另外针对煤化工行业的环保、操作规程、技术装备、工程建设等标准空白较多。现阶段,标准化工作的任务仍以新标准的研发为主,应以煤化工产业的总体发展及相关国家政策为导向,加快单位产品能耗限额、取水定额、三废排放及治理、清洁生产等节能环保类标准以及装备技术类标准的制修订工作,通过标准的建立规范和引导产业绿色、健康发展。另一方面,在推进煤炭清洁高效利用技术相关标准建立的同时,应注重加强煤化工产业与发电、油气化工、钢铁、建材等其他行业的联系并建立相关的技术标准。未来在以政府为主导、企业团体协调配合的新型标准体系的支撑及"一带一路"战略的引领下,先进、完善的标准化体系将更好地助力煤化工产业的发展。     

C4烃类含氧化合物脱除工艺研究进展

综述了现行C4烃类化合物中含氧化合物脱除的工艺方法--精馏法和吸附法,对不同脱除工艺的工业应用状况进行了分析比较,提出吸附分离工艺是一个重要的发展方向.     

现代煤化工产业的现状及展望

综述了我国现代煤化工行业的现状,着重介绍了煤制天然气、煤制油、煤制甲醇、煤制二甲醚和煤制烯烃产业的工艺流程、技术特点、装备状况和发展前景,分析、比较了主要产业的环境承载力,并根据我国煤炭资源和生产消费的特点对该行业的发展提出了建议。     

国内煤化工的现状及发展

介绍了国内煤化工行业的现状,详细介绍了煤制油、煤制烯烃、煤制天然气、煤制乙二醇、煤制芳烃项日的技术、经济情况,指出通过开发下游产品,合理利用CO2来改善产品单一、节能减排压力大问题。     

我国煤化工产业的技术发展现状

针对目前石油供应量与消费量之间矛盾突出、石油对外依存度较高的问题,对我国煤制油、煤制烯烃、煤制天然气的技术现状进行了分析,并据此找到了发展新型煤化工产业的有效途径,以满足国内能源需求,降低煤炭对环境的污染,实现清洁能源的有效利用。     

重庆地区新型煤化工发展

针对重庆地区煤质资源特点及结合目前市场实际情况,提出在此地区可以发展新型煤化工产业,如煤气化生产甲醇、煤气化联合循环发电、煤间接液化,不仅可以减轻燃煤和传统煤化工行业造成的环境污染而且可以带来较好的经济效益,并提出了新型煤化工产业的可行性工艺,发展新型煤化工行业在重庆有着广阔前景。     

煤化工的精细化产业发展现状及建议

受低油价的冲击和国家经济转型的影响,经过多年快速发展的现代煤化工项目存在的盲目发展、产品同质化严重、经济效益不突出和环保压力大等问题日益突出,煤化工产品市场面临产能过剩局面,煤化工产业的健康可持续发展受到影响。精细化产业发展以市场需求为导向,可以实现煤化工产业链差异化、高端化发展,是解决煤化工发展问题的重要手段,也是未来煤化工产业的发展趋势。介绍了煤制油、煤制烯烃、煤制乙二醇、煤制天然气及煤制芳烃等现代煤化工项目产业链及精细化发展的情况,指出了我国煤化工精细化发展的未来趋势,并提出促进煤化工精细化发展的建议。     

煤化工技术进展及产业现状分析

现代煤化工的发展符合我国油、气短缺,煤炭相对丰富的国情。分析了国家相关煤化工产业政策,综述了煤气化、煤制天然气、煤制油、甲醇、甲醇制烯烃等煤化工领域的技术进展及产业现状。尽管我国煤化工产业的发展面临一些问题、存在一些不确定性因素,但总体来讲,以科学发展观为统领的现代煤化工的健康、和谐、可持续发展仍然具有较好的前景。     

浅谈新型煤化工火炬放空系统

煤化工是以煤为原料,经过化学加工使煤转化为气体、液体、固体燃料以及化学品的过程。煤化工分传统和新型两种,传统的涉及煤焦化、煤电石、煤合成氨(化肥)等领域,新型煤化工通常指煤制油、甲醇、二甲醚、烯烃四种。目前我国新型煤化工行业正在呈现扩大规模、联产联建、深加工的特点。为了保证装置系统运行符合国家安全及环保要求,通常设置火炬系统处理各种工况下的火炬气,但新型煤化工的火炬系统是区别于石油炼制企业的火炬放空系统。     

Uncharged atomic oxygen in oxidative conversion of C1-C2 alkanes

The role of uncharged atomic oxygen species in oxidative conversion of CH₄ and C₂H₆ has been considered. It is shown that active atomic oxygen species participate in C₁---C₂alkanes conversion in the presence of NO on zeolites, in the CH₄N₂O¹ and CH₄---O₂ systems on transition metal silicides and nitrides, as well as hydrocarbon oxidation during N₂O and O₃ photolysis by excimer laser light. Participation of uncharged oxygen species in conversion of light alkanes makes it possible to explain not only hydrocarbon formation pathways, but those of oxygen-containing compounds as well.     

榆林市甲醇产业现状及发展建议

为研究甲醇产能释放后对区域经济效益的影响,介绍了榆林市甲醇产业发展历程、现状,分析了榆林甲醇工业发展的影响条件,阐述了榆林市甲醇产业发展的有利因素和不利因素,提出了榆林甲醇产业发展建议。陕西榆林煤炭资源丰富,交通发达,目前年产60万t以上的甲醇建成和在建的项目已达7个,随着部分在建项目的陆续投产,榆林将成为全国最大的甲醇生产基地。针对榆林甲醇工业发展面临的水资源短缺、人才短缺、人力资源流失、增加值能耗较高、环保形势严峻等问题,提出未来应积极发展甲醇下游产品,延伸产品链,提高附加值;在甲醇生产中大力推广节能技术,合理选址下游产业,合理开发人力资源;加强宏观调控,加大三废治理力度。     

NiFeAlO4载氧体制备及煤化学链燃烧反应特性

铁基载氧体是一种具有工业应用前景的载氧体,但存在氧利用率低、在高温下易烧结等问题。虽可通过制备双金属复合载氧体或添加惰性组分改进其性能,但均存在一定缺陷。若将活性组分和惰性材料融入到一个晶体结构制备尖晶石结构载氧体,则可实现利用双金属协同作用提高载氧体活性的同时,利用Al3+提高载氧体的稳定性。采用共沉淀法和溶胶凝胶法制备了具有尖晶石结构的NiFeAlO₄载氧体,考察了制备方法、载氧体与煤质量比对NiFeAlO₄载氧体化学链燃烧特性和循环稳定性的影响,并分析了载氧体对煤转化过程的作用。结果表明,溶胶凝胶法制备的NiFeAlO₄载氧体具有更好的反应性,载氧体与煤质量比为20∶1时,碳转化率为86.7%,远高于煤单独热解时的碳转化率(34%),此时CO₂体积分数为93.6%。对反应前后NiFeAlO₄载氧体晶相结构和形貌进行分析,表明循环过程中经“还原-氧化”后生成的NiO和载氧体颗粒团聚是导致载氧体活性下降的主要原因。相较于载热作用,NiFeAlO₄载氧体在煤化学链燃烧中主要起供氧作用,其不仅会促进挥发分向煤气的转化,且NiFeAlO₄载氧体与焦炭之间也存在固-固反应,利于更多CO₂的生成。     

CDM-系列开窗导流式催化精馏模块在C4/C5醚化等反应中的工业应用

CDM-系列开窗导流式催化精馏模块具有优异的催化反应和组分分离双重功能,综合性能优于催化蒸馏组件CDP,是其升级换代产品。可应用于甲基叔丁基醚、轻汽油醚化、异丁烯叠合和叔丁醇脱水等工艺中,主要介绍CDM-系列开窗导流式催化精馏模块产品特点及在工业装置中的应用情况。     

Catalytic reactions of C1 and C3 hydrocarbons in the presence of oxygen and oxygen-containing compounds

The reaction rates and selectivity of lower olefines formation in high temperature reactions, such as catalytic methane dehydrodimerization and catalytic pyrolysis of C₃ hydrocarbons are substantialy enhanced by oxygen and oxygen-containing compounds.     

Non-premixed fluidized bed combustion of C1-C4n-alkanes

The non-premixed combustion of C₁-C₄n-alkanes with air was investigated inside a bubbling fluidized bed of inert sand particles at intermediate temperatures: 923 K ? T_B ? 1123 K. For ethane, propane and n-butane, combustion occurred mainly in the freeboard region at bed temperatures below T₁ = 923 K. On the other hand, complete conversion occurred within 0.2 m of the injector at: T₂ = 1073 K. For methane, the measured values of T₁ and T₂ were significantly higher at 1023 K and above 1123 K, respectively. The fluidized bed combustion was accurately modeled with first-order global kinetics and one PFR model to represent the main fluidized bed body. The measured global reaction rates for C₂-C₄n-alkanes were characterized by a uniform Arrhenius expression, while the global reaction rate for methane was significantly slower. Reactions in the injector region either led to significant conversion in that zone or an autoignition delay inside the main fluidized bed body. The conversion in the injector region increased with rising fluidized bed temperature and decreased with increasing jet velocity. To account for the promoting and inhibiting effects, an analogy was made with the concept of induction time: the PFR length (b_i) of the injector region was correlated to the fluidized bed temperature and jet velocity using an Arrhenius expression. These results show that the conversion of C₂-C₄n-alkanes can be estimated with one set of critical bed temperatures and modeled with one Arrhenius kinetics expression.     

碳四烯烃制丙烯催化剂及其工业应用

研究碳四烯烃催化裂解制丙烯BOC-1催化剂的放大制备及其工业应用,详细介绍催化剂放大制备后实验室小试和工业应用评价结果。BOC-1催化剂在工业生产装置中运行和再生性能良好,丙烯单程收率28.5%,碳四烯烃转化率82.1%,催化剂使用周期17天,各项性能指标均超过洛阳炼化宏力化工有限责任公司的工业催化剂水平,适合进一步推广使用。建立由烯烃催化裂解、吸收稳定、气分、MTBE醚化和烷烃分离5个单元组成的碳四烯烃资源综合利用工艺流程,并使用VMGSim流程模拟软件进行模拟计算。结果表明,采用新工艺流程,碳四烯烃综合利用率99.3%,聚合级丙烯收率35.19%。     

Synthesis of cyclic carbonates from epoxides: Use of reticular oxygen of Al2O3 or Al2O3-supported CeOx for the selective epoxidation of propene

Reticular oxygen of Al₂O₃ or CeO_x supported on Al₂O₃ was used for the epoxidation of propene without any double bond cleavage. In batch reaction, Al₂O₃ alone was able to convert propene into propene oxide (PO) with 100% selectivity and 2% conversion of propene with a close to 3:1 ratio with respect to the number of Al(III) reduced to elemental Al. When Ce₂O₃/Al₂O₃ or CeO₂/Al₂O₃ was used, Al remained in its +3 oxidation state, while the Ce oxide was the oxidant as demonstrated by XPS analyses. CeO_x/Al₂O₃ was more active (propene conversion yield of 4–5%) but the selectivity was lower (70%) as PO was isomerized into acetone and propionaldehyde.

Interestingly the use of reticular oxygen very much improves the selectivity with respect to the use of pure O₂. In fact, while propene was more efficiently oxidized (10%) with O₂ in presence of Al₂O₃ or CeO_x/Al₂O₃, the selectivity was as low as 40% because C1 and C2 products were formed. However, the use of reticular oxygen represents a selective two-step technique for the use of molecular oxygen as oxidant of propene. The used oxides can be re-oxidized and the whole process can be further improved towards higher yields.

PO is quantitatively converted into propene carbonate by reaction with CO₂ in presence of Nb₂O₅.     

Electrochemical activity, stability and degradation characteristics of IrO2-based electrodes in aqueous solutions containing C1 compounds

In this paper, we investigate the electrocatalytic behavior and degradation characteristics of IrO₂-based electrodes in Na₂SO₄ solutions containing C₁ compounds (CH₃OH, HCHO and HCOOH). Decreases are generally observed in the electrochemically active area, electrochemical stability and durability of the electrodes in aqueous solutions in the presence of these organic substrates. The following sequence holds for the influence of C₁ compounds on the electrode properties (i.e. activity and stability): CH₃OH > HCHO > HCOOH. The corrosion characteristics of electrode are studied by X-ray diffraction measurements. For the first time, the decomposition and dissolution of active oxide layers are quantitatively characterized from the decreases in cell volume of rutile-structured IrO₂ crystallite and from the increases in texture coefficient of (0 0 2) planes, respectively, as a result of the accelerated lifetime tests.     

A novel nickel/carbon catalyst for CH4 and H2 production from organic compounds dissolved in wastewater by catalytic hydrothermal gasification

A novel Ni/carbon catalyst recently developed by the authors was used to gasify organic compounds dissolved in the wastewater with TOC concentration from 0.2 to 2%. The process removes the organic compounds by gasifying them into high calorific gases like methane and hydrogen. The investigations were focused on the efficiency of the Ni/carbon catalyst in terms of carbon conversion, conversion of big organic molecules, and catalyst deactivation due to sintering. The preliminary results showed that up to 99% carbon conversion can be achieved at 360 °C, and 20 MPa. A conversion mechanism was suggested which consists of: first, decomposition of big molecules to small molecules on the metal surface, steam gasification of small molecules to produce CO and H₂ followed by CO methanation and CO shift reaction to produce CH₄ and CO₂. The catalyst was found to be highly active and stable and no sintering was observed even after 100 h of reaction time.