脱酯脱醛工艺在煤制乙二醇装置中的应用问题分析及解决措施

在煤基合成气制乙二醇(SEG)的反应过程中，会发生多种副反应、生成多种副产物，其中，微量的酯类、醛类物质对乙二醇产品紫外线透光率造成很大影响。通过技术改造增设脱酯、脱醛装置，对产品精馏塔侧线采出的乙二醇进行脱酯脱醛处理。实际运行数据表明，脱酯、脱醛后乙二醇220 nm紫外线透光率平均能提升6%～14%,275 nm紫外透光率平均能提升8%～15%。介绍了煤制乙二醇脱酯、脱醛装置的树脂装填、装置开停车、树脂保护，脱酯脱醛装置运行经验及控制，可为乙二醇生产厂家进行产品质量提升提供参考和借鉴。     

合成气经草酸二甲酯制乙二醇的技术进展

论述了合成气经草酸二甲酯制乙二醇的开发历程、工艺原理以及工业化装置取得的技术进展。指出应根据合成气经草酸二甲酯制乙二醇的特点制定相应的产品标准,不断优化技术细节,提高合成气经草酸二甲酯制乙二醇的竞争力。     

合成气制乙二醇产品品质提升方法的应用研究

在乙二醇合成工艺路线中，合成气制乙二醇生产装置的聚酯级乙二醇产出率低。通过对乙二醇精馏系统进行分析，设计乙二醇液相加氢系统，采用原精馏系统与液相加氢系统深度融合技术，将乙二醇杂质含量降低，使合成气制乙二醇生产装置产出的工业级乙二醇产品全部或大部分转化为聚酯级乙二醇，显著提高了企业的经济效率。     

合成气制乙二醇生产工艺技术比较及经济性分析

本文对目前国内外合成气制乙二醇主要工艺技术进行比较,分析不同技术的特点,并以200kt/a合成气制乙二醇装置为例进行经济性分析,最终得出其生产的可行性。     

湖北化肥合成气制乙二醇装置通过竣工验收

正2015年11月10日,中石化湖北化肥20万t/a合成气制乙二醇工业示范装置通过竣工验收。该装置原料CO和H2来自现有壳牌粉煤气化制合成氨装置富余的合成气,采用中石化自主开发的合成气草酸酯路线制乙二醇技术。该项目2012年8月开工,2013年11月中产,2014年3月开车成功,产出优质乙二醇产品。     

合成气综合利用分析

国内某石化公司建有一套部分氧化/气电联产(IGCC)装置作为全厂公用工程岛,为工艺装置提供氢气、蒸汽、电等公用工程介质。IGCC装置部分氧化单元所产粗合成气经处理后1/4用于制氢、3/4用于发电,由于电价较低,合成气发电经济效益较差。本文通过对IGCC装置所产合成气的价值进行估算,提出合成气制氢、合成气制甲醇、合成气制丁辛醇、合成气制乙二醇等综合利用途径,并对合成气制氢、甲醇、丁辛醇、乙二醇等各种途径的主要技术及经济性进行对比、分析,提出了合成气综合利用的建议。     

乙二醇生产过程中CO偶联生产草酸二甲酯工艺优化

煤基原料制乙二醇是替代石油化工的一条重要途径,淮化集团有限公司与华东理工大学、上海浦景化工技术有限公司合作,建设年产十万吨合成气制乙二醇工业示范项目,2016年5月装置一次开车成功,生产出合格聚酯级乙二醇产品,"合成气制乙二醇技术"是以CO、H_2和O_2为主要原料,经中间产品草酸二甲酯,间接合成乙二醇的新技术,由于我国能源的基本国情,在可预见的将来"合成气制乙二醇技术"必将在我国发展成为替代采用传统石油原料的"EO/EG技术"的乙二醇制备路线",根据公司年产十万吨合成气制乙二醇工业示范项目运行特点,重点探讨温度、压力、配料比等关键因素对CO偶联生产草酸二甲酯工艺过程的影响,提出了草酸二甲酯生产工艺优化。探索乙二醇装置反应的能耗及经济性。     

新疆天业合成气制乙二醇新装置开车成功

<正>新疆天业集团有限公司新建的合成气制乙二醇新装置总产能为20万吨/年,由4条生产线组成,新装置采用日本宇部兴产和高化学株式会社技术。2015年3月下旬,新装置的第一条5万吨/年生产线开车成功,后续另外三条生产线计划陆续开车。此前2013年投产的新疆天业的5万吨/年合成气制乙二醇装置的产品已经达到聚酯级的需求,产品基本供应聚酯工厂,解决了合成气制乙二醇成功应用于聚酯行业的难题。     

湖北化肥20万t/a合成气制乙二醇成套技术通过鉴定

<正>2017年11月28日,湖北化肥20万t/a合成气制乙二醇成套技术通过中国石化鉴定,建议加快推广应用,让科技转化为生产力。湖北化肥20万t/a合成气制乙二醇示范装置是中国石化十条龙攻关项目之一,采用中国石化自主研发的专有成套技术。湖北化肥作为攻关组长单位,与上海石油化工研究院、上海工程公司等6家单位,组成攻关小组,开发合成气制乙二醇装置工艺包;完成各     

影响合成气制乙二醇质量关键指标的因素及控制方法

紫外透光率(简称UV值)、乙二醇纯度、醛含量是评价合成气制乙二醇产品质量的关键指标。针对合成气制乙二醇企业在生产运行过程中普遍存在的关键指标不稳定、装置长时间运行后UV值下降的现象,主要探讨了精馏分离系统的温度、真空度、副产物的采出以及粗乙二醇进料质量等因素对合成气制乙二醇关键指标的影响,进一步提出了在生产运行过程中的控制要点及采取的辅助措施。     

Polymers for information storage systems. II. Polymerization kinetics for preparation of highly crosslinked polydimethacrylates

Polymers of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate were prepared by photoinitiated polymerizations in the presence of 2,2-dimethoxy-2-phenyl-acetophenone at 27°C. The reactions led to highly crosslinked polymeric networks. The volume shrinkage observed during polymerization was a function of the number of ethylene glycol units in the dimethacrylate monomer. The kinetic rate constants of polymerization, as determined from the photopolymerization characteristics using a dilatometric technique, were again dependent on the number of ethylene glycol units in the monomer. The importance of these results on the crosslinked structure of the prepared networks is discussed.     

Synthesis and Ion-Binding Properties of Polymeric Pseudocrown Ethers: A Molecular Dynamics Study

Abstract

A novel method for producing inexpensive polymeric pseudocrown ethers in situ during free-radical polymerizations was investigated using molecular dynamics simulations. This scheme is based upon a template ion and exploits the tendency of oligomeric ethylene glycol diacrylates to form intramolecular cycles during polymerization. In the scheme, a template ion is used to induce the poly(ethylene glycol) diacrylates (PEGDA) to assume cyclic structures before polymerization with a comonomer. Experimental studies demonstrated that certain salts that were insoluble in nonpolar solvents were solubilized upon the addition of oligomeric poly(ethylene glycol) (PEG) due to complexation. Further evidence of cation binding by oligomeric PEG was obtained by ¹H NMR studies of PEG and its complexes with metal salts. To optimize the template ion synthesis approach, molecular dynamics simulations were performed on PEGDA containing between two and ten ethylene glycol repeating units, with and without the presence of cations. Simulation results indicated that the presence of the templating cation significantly decreased the mean end-to-end distance, thereby bringing the unsaturated endgroups into close proximity. The PEGDA ligand that resulted in the most effective templatization for Na⁺ contained four ethylene glycol repeating units. Simulation times greater than 50 ps had little effect on the results for ligands containing 7 or fewer ethylene glycol repeating units.     

新戊二醇生产工艺研究进展

新戊二醇及其衍生物具有良好的耐水性、耐热性和耐光性,这些优良的特性使新戊二醇具有广泛的应用领域。新戊二醇工业上采用甲醛和异丁醛缩合合成,歧化法用液碱催化缩合,加氢法先用三乙胺催化,然后进行催化加氢。加氢法在产品质量、经济指标和环保要求方面均优于歧化法,因此,建议改进现有歧化法工艺装置,新建装置尽可能采用加氢法。     

Unsaturated polyesters based on terephthalic acid: 1. Proton magnetic resonance spectrum of poly(propylene terephthalate) prepolymer

Peaks in the proton magnetic resonance spectrum of the prepolymer prepared by the polyesterification of terephthalic acid with excess propylene glycol are assigned to the methyl, methylene and methine protons in propylene glycol units which may exist in four different environments. The assignments are confirmed by removing the excess propylene glycol from the prepolymer, by benzoylating the prepolymer, and by obtaining spectra for isopropanol, isopropyl benzoate, propylene glycol 1,2-dibenzoate, propylene glycol, and bis(2-hydroxypropyl) terephthalate.     

Preparation and hydrolytic degradation of sulfonated poly(ethylene terephthalate) copolymers

A series of poly(ethylene terephthalate-co-ethylene 5-sodiosulfoisophthalate) copolyesters containing from 1 up to 50 mol% of sulfonated units was prepared by melt polycondensation from ethylene glycol and mixtures of dimethyl terephthalate and dimethyl 5-sodiosulfoisophthalate. The resulting copolymers had a random microstructure and contained oligo(ethylene glycol) units in amounts increasing with the content in sulfonated isophthalate units. Copolyesters with more than 20 mol% of 5-sodiosulfoisophthalic units were amorphous and easily soluble in water. The hydrodegradability of the copolyesters was very high as compared to poly(ethylene terephthalate), and increased with the content in sulfonated units. It was demonstrated that the susceptibility to acidic hydrolysis of these copolymers is mainly due to the presence of the sodium sulfonate groups, the influence of the oligo(ethylene glycol) units in this regard being noticeable but limited.     

Immobilized Phosphate Ligands with Enhanced Ionic Affinity through Supported Ligand Synergistic Interaction

Abstract

The ability of a secondary group to influence the metal ion affinities of a primary ligand immobilized on crosslinked polystyrene beads is reported. The secondary groups were glycol units, ‐(CH₂CH₂O)_1‐4‐, and their effect on phosphate ligands was studied. The affinities of Pb(II), Cd(II), Cu(II), Ni(II), Zn(II), Fe(III), Y(III), La(III), Eu(III), Lu(III), and U(VI) were quantified from HNO₃, HCl, and H₂SO₄ solutions in concentrations up to 4 N. Affinities were highest for U(VI) and the trivalent ions. The glycol units enhanced the extent of metal ion complexation by the phosphate ligands through coordination of the metal ion and not through an auxiliary group effect (where there would be a direct interaction between the glycol units and the phosphate ligand) as indicated by the similarity in the FTIR spectra of the four phosphorylated glycol resins. At least two glycol units are needed for synergistic cooperation between the glycol and phosphate in binding metal ions.     

耦合SOEC的煤制乙二醇新工艺开发与系统评价

针对传统煤制乙二醇过程CO₂排放高和资源利用率低等问题,本文提出了一种耦合固体氧化物电解池（SOEC）的煤制乙二醇新工艺（SO-CtEG）。新工艺通过集成固体氧化物电解池制氢技术,避免了水煤气变换单元和空分单元,也有效降低了煤气化和酸性气体脱除单元的处理规模。在全流程建模与模拟的基础之上,进行了详细的技术经济分析与灵敏度分析。结果表明,SO-CtEG新工艺的碳元素利用效率和?效率分别是传统煤制乙二醇项目的2.16倍和1.48倍。与传统煤制乙二醇过程相比,SO-CtEG新工艺总投资费用降低23.64%、生产成本节约17.14 %,内部收益率提高8.85%。因此,新工艺不但可以提高风光消纳能力和减少传统煤制乙二醇的碳排放,还具有更佳的技术经济环境性能,是未来煤制乙二醇行业具有良好发展前景的工艺路线之一。     

煤制乙二醇关键单元技术与低碳集成工艺的研究进展

我国乙二醇对外依存度居高不下,而富煤少油的资源特性使得我国煤制乙二醇技术具有较好的成本与原料优势,发展迅速。本文综述了国内外煤制乙二醇技术的技术现状和发展趋势,重点介绍了煤气化、草酸二甲酯合成和乙二醇合成与精制等关键单元技术的技术特征、工艺流程和技术进展,并分析了相关单元对整个煤制乙二醇系统技术经济性能的影响。针对现有煤制乙二醇技术存在能耗高、质能效率低和CO₂排放大的问题,着重讨论了集成CO₂高效利用的煤与富氢资源联供制乙二醇集成工艺的进展,包括耦合焦炉气、页岩气和绿氢等资源的新工艺等。以焦炉气为例,集成不同重整技术的新工艺使得传统工艺的碳效率和?效率分别提升了23.35%~39.17%和4.25%~10.12%,生产成本降低了8.73%~19.88%,内部收益率提高了3.6%~9.6%。因此,集成富氢资源与CO₂高效利用的煤制乙二醇创新工艺是该行业向高效-经济-清洁可持续发展的重要方向。     

Sequential distribution of main chain phosphorus-containing copolyesters characterized by 1H NMR

A series of main chain phosphorus-containing copolyesters were synthesized by polycondensation of terephthalic acid (TPA), ethylene glycol (EG) and phenyl phosphonic acid (PPA). Chemical structures of these main chain phosphorus-containing copolyesters were characterized by ¹H NMR. Experimental results show that the resonance intensity of PPA aromatic protons increases with increase of the phosphorus content. The chemical shifts of the ethylene protons in the ethylene glycol units vary with different sequences. The resonance chemical shift of the ethylene protons of the T-E-T unit is higher than those of P-E-T (T-E-P) and P-E-P units. The monomer molar fraction, sequential distribution and degree of randomness of the phosphorus-containing copolyesters were determined through analyses of the ethylene protons in the ethylene glycol units. The molar fractions of the PPA comonomer determined by ¹H NMR analyses are close to the values determined by a UV method. The degree of randomness for the copolyesters was found to be in the range 0·66–0·83. © 1998 SCI.     

Telechelic polyesters of ethane diol and adipic or sebacic acid by means of bismuth carboxylates as non-toxic catalysts

Dimethyladipate or dimethylsebacate were polycondensed with an excess of 1,2-ethane diol in bulk using two different temperature/time programs. Bismuth(III)n-hexanoate (BiHex₃), tin(II)2-ethylhexanoate (SnOct₂) and titanium tetrabutoxide were used as catalysts. Only the bismuth catalyst yielded clean telechelic polyesters having two ethylene glycol endgroups. With SnOct₂ cyclic oligoesters were obtained as byproducts. Ti(OBu)₄ yielded OH-terminated linear chains containing large amounts of diethylene glycol units (detectable up to three ether groups per chain). Furthermore, small amounts of cycles were also formed. Acid-catalyzed polycondensations of ethylene glycol with sebacic acid gave low yields of low oligomers, part of which contained diethylene glycol units.