邻苯二酚技术进展与市场分析

分析了国内外邻苯二酚生产和消费状况。介绍了邻苯二酚的合成方法，目前其主要的生产方法为苯酚过氧化氢羟基化法，并提出了一些发展建议。     

国家技术创新项目600t/a苯酚羟基化制邻苯二酚生产装置在徐州建成投产

邻苯二酚是农药克百威（呋喃丹）、残杀威、乙霉威的重要中间体，也是生产香兰素、胡椒醛等香料的重要原料，还可生产对叔丁基邻苯二酚阻聚剂和抗氧剂、医药及其它精细化学品，市场需求量较大，预计我国“九五”末期每年约需邻苯二酚７０００ｔ。目前，国际上只有法国、意大利、日本等几个发达国家能够采用苯酚羟基化的先进技术生产邻苯二酚，但都不对外转让技术。多年来，我国邻苯二酚一直依赖进口，耗费不少外汇。因此，国家在“八五”期间已将邻苯二酚列入攻关计划，虽经有关人员奋力攻关，但都未能达到预期目的。南开大学、化工部科学技…     

中国建成苯酚羟基化法制邻苯二酚生产装置

邻苯二酚是生产呋喃酚的主要原料，也是生产香兰素、胡椒醛等香料的主要原料，此外，还可生产对叔丁基邻苯二酚阻聚剂和抗氧剂及其它精细化学品，目前我国需求量约为７０００ｔ／ａ。南开大学和化工科研总院、江苏神农化工集团铜山精细化工总厂在小试成功的基础上，按分子设计和化工新技术开发程序利用苯酚羟基化法建成６００ｔ／ａ邻苯二酚生产装置，该装置具有成套性强、流程短、投资少、邻苯二酚的选择性和收率高等特点，产品质量优良。中国建成苯酚羟基化法制邻苯二酚生产装置@李海屏     

邻苯二酚技术进展与市场分析

邻苯二酚是一种重要的精细化工中间体。世界上邻苯二酚生产能力约为3．8万t／a，2004年产量约为3．1万t。2004年我国邻苯二酚产量约为1500吨，表观消费量达到7287吨；2005年产量约为2800t，表观消费量达到9077吨。目前国内仅有连云港三吉利化工有限公司生产邻苯二酚，产能3000t。预计2008年我国邻苯二酚的需求量将达到1138万吨。     

邻苯二酚的研究进展及市场前景

邻苯二酚是一种重要的精细化工中间体。广泛用于农药、香料、医药、对叔丁基邻苯二酚阻聚剂的合成，以及染发剂、橡胶硬化剂、杀菌剂等领域。2004年我国邻苯二酚产量约为1500吨，表观消费量达到7300吨。含量99％的邻苯二酚市场售价约为36500元／吨。目前国内仅有连云港三吉利化工有限公司生产邻苯二酚。预计2008年我国邻苯二酚的需求量将达到1．38万吨。因此，国内有关单位有必要积极研究对策，以促进我国邻苯二酚产业的发展。     

徐州建成邻苯二酚装置

南开大学、化工科研总院、江苏神农化工集团铜山精细化工总厂日前在徐州建成年产６００吨苯酚羟基化制邻苯二酚生产装置，并投入生产。邻苯二酚是农药生产过程重要的中间体，也是生产香兰素、胡椒醛等香料的重要原料，还可生产对叔丁基邻苯二酚阻聚剂和抗氧剂及其它精细化学品。目前我国每年需求量约为７０００吨左右。他们在南开大学小试获得成功的基础上，按分子设计和化工新技术开发程序，建成该套装置。该装置具有成套性强、流程短、投资省、邻苯二酚选择性和收率高、产品质量优良等特点。徐州建成邻苯二酚装置     

中间体与精细化工文摘

国内邻苯二酚的生产及消费 文摘:本文介绍邻苯二酚的生产及消费。1.邻苯二酚生产新技术:国内大部分厂家采用邻氯苯酚碱解法生产邻苯二酚,此法为落后方法,新的生产技术有(1)苯酚羟基化法:以苯酚和过氧化氢为原料,磷酸盐、氧化钾等为催化剂,直接在苯酚上的邻位和对位发生羟基化反应,生成邻苯二酚和对苯二酚,然后经分馏精制     

邻苯二酚的开发与应用

邻苯二酚是采用绿色工艺生产药物中间体的最典型的实例。以过氧化氢为氧化剂的苯酚羟基化可以生产邻苯二酚和对苯二酚，由于流程简单，原料易得，反应条件温和，过氧化氢价廉，氧化副产物是水，不会造成环境污染，是21世纪最有前途的“清洁”工艺。     

投资邻苯二酚正当时

邻苯二酚是重要的有机中间体 ,国内市场供需缺口很大 ,年需求量达 65 0 0t左右 ,其中 80 %用于农药生产 ,其余主要用于香料香兰素生产。预计近几年在克百威、残杀威领域邻苯二酚的年需求增长速度将超过 7%。我国是世界主要香兰素生产和出口国 ,预计今后该领域邻苯二酚的需求潜力很大。邻苯二酚还广泛用于聚苯乙烯、聚丁二烯的阻聚剂 ,聚合物、油品的抗氧剂以及有机化合物的光稳定剂等 ,我国目前年产量仅约 10 0t,消耗邻苯二酚较少 ,制约其发展的主要原因是邻苯二酚产量少、价格高。由于国内邻苯二酚产不足需 ,进口产品在国内市场占有很大份…     

罗地亚在中国建联苯酚装置

罗地亚（Rhodia）将投资3500万美元，在上海附近建设一套联苯酚装置，产能1．2万t／a．2007年初建成。新装置将生产联苯酚、邻苯二酚和氢化醌。罗地亚在上海有三座工厂，生产联苯酚衍生物。在无锡与日本宇部合资生产邻苯二酚衍生物邻甲氧基苯酚及香精和香料组分异冰片基环己醇（IBCH）。     

愈创木酚的制备研究进展

愈创木酚是合成香料、药物及植物生长调节剂等的重要中间体,而其生产和制备仍存在诸多问题。对从天然物中提取愈创木酚、生物发酵和化学合成制备愈创木酚的方法及进展进行介绍,指出邻甲氧基苯胺制备愈创木酚的关键是连续生产工艺的开发和剩余硫酸铜及硫酸的再利用;邻苯二酚制备愈创木酚中应摒弃毒性较大的硫酸二甲酯,选取腐蚀性和毒性较小的甲醇和碳酸二甲酯为甲基化试剂,开发低温、高活性、长寿命的催化剂和设计开发快速再生催化剂技术是实现邻苯二酚合成愈创木酚工业化有效途径,并认为环氧环己烷制备愈创木酚是一种较有前途的生产方法。     

Biodegradation of catechol by Pseudomonas fluorescens isolated from petroleum‐impacted soil

Bioremediation strategies have been applied to clean up petroleum hydrocarbon (PHC) impacted sites. Introducing PHC degrading microorganisms (bioaugmentation) and enhancing the in‐situ nutrients availability (biostimulation) are widely used strategies. These strategies can be combined to lead to a better bioremediation performance. In this work, Pseudomonas fluorescens was isolated from a PHC impacted site. Through a 2³ factorial design plan, the effect of various combinations of nitrate, sulphate, and phosphate ions on the PHC bioremediation performance by P. fluorescens was investigated using catechol, an essential metabolic intermediate of BTEX degradation, as the sole carbon source. The maximum specific catechol degradation rate was chosen as the response to evaluate the catechol bioremediation performance. The ANOVA results indicated that the presence of nitrate ions alone lowered the maximum specific catechol degradation rate, which can be explained by the accumulation of nitrites and ammonia during the denitrification process by P. fluorescens. It was noted that dosing sulphate ions alone did not affect the bioremediation performance, which indicates P. fluorescens can grow in a sulphur‐limited environment. In contrast, the presence of sulphate and nitrate ions together can lead to a higher specific catechol degradation rate. This may be caused by the presence of sulphate that can suppress the production of nitrites. The importance of phosphate ions on catechol biodegradation was investigated. The absence of phosphate led to incomplete biodegradation. Introducing phosphate ions can accelerate catechol degradation, which can be explained by the secretion of organic acids.     

邻苯二酚与甲醇合成愈创木酚的热力学分析

邻苯二酚与甲醇气相单醚化合成愈创木酚因经济、环保、原料廉价易得、可实现连续化生产等优点而备受关注。为了有效利用资源,对该反应过程进行了较为详细的热力学分析。根据邻苯二酚(catechol)、甲醇、愈创木酚(guaiacol)及水的标准摩尔生成焓Δ_fH^θ_m、标准熵变ΔS^θ_m和热熔C_p,m等热力学数据,讨论了温度对邻苯二酚与甲醇气相合成愈创木酚反应的焓变Δ_rH_m、自由能变Δ_rG_m及平衡常数K的影响。结果表明,在400～800 K温度范围内,该反应是一个放热自发反应,可在较低温度下顺利进行,有较大反应平衡常数。因此,该反应的研究关键主要是较低温度下高活性催化剂的研发和最适宜反应条件的选择。     

活性炭负载乙酸钾催化邻苯二酚和乙醇合成邻羟基苯乙醚

以活性碳为载体,以乙酸钾为活性组分的固体碱催化剂对邻苯二酚与乙醇气固相催化合成邻羟基苯乙醚的过程,考察了乙酸钾负载量对催化剂活性的影响以及反应条件对该反应的影响。结果表明随乙酸钾负载量的增加催化剂的碱性先增加后减小,乙酸钾负载量为15%质量分数的催化剂对该反应有最好的催化性能,当反应温度为433 K,邻苯二酚和乙醇摩尔比为10时,反应时间为150 min较适宜。在此条件下,邻苯二酚的转化率和邻羟基苯乙醚的选择性分别为99%和97%。     

Application of electrosynthesized poly(aniline-co-p-aminophenol) as a catechol sensor

Poly(aniline-co-p-aminophenol) (copolymer) film was used as a sensor to determine the presence of catechol, taking advantage of the ability of the film to effectively catalyze the oxidation of catechol. The copolymer served as an electron transfer mediator between the electrode surface and catechol in the solution. The response current of the catechol sensor depended on the applied potential, pH and temperature at a given concentration of catechol. At optimum conditions, the catechol sensor displayed an excellent electrocatalytic response to the detection of catechol in a concentration range from 5 to 500 μM with a detection limit of 0.8 μM. The effects of selected organic compounds on the response of the catechol sensor were studied. Together, these findings show that the catechol sensor exhibits a better selectivity towards interfering species and a better operational and storage stability.     

Utilizing the phenol byproducts of coke production 4. Energy-saving synthesis of effective polymerization inhibitors for the processing of liquid pyrolytic products

Experimental data are presented for the oxidative oligomerization of phenol byproducts from coke production by alkali-metal persulfates, so as to obtain an effective inhibitor of the thermopolymerization of liquid pyrolytic products. The product exhibits strong inhibiting properties in the heat treatment of pyrocondensates and matches the effectiveness of the well-known inhibitor tert-butyl catechol, which is a sterically hindered diatomic phenol.     

Catechol-containing waterborne polyurethane adhesive inspired by mussel proteins

A series of waterborne polyurethane (PDMAPU) containing catechol group were prepared by double-bond random copolymerization of terminated double bond polyurethane prepolymer with modified acrylamido dopamine under thermal initiation. This kind of mussel-like waterborne polyurethane adhesive is inspired by marine mussel, as well as it is environment-friendly and used in bonding of leather. FTIR and ¹H NMR proved the successful introduction of catechol group into polyurethane matrix. Oxidative cross-linking between catechol unit and molecular chain in PDMAPU structure, the thermal stability and crystallization ability of PDMAPU was significantly improved. The increase of the particle size of PDMAPU emulsion showed that the introduction of catechol group changed the microstructure of polyurethane and enhanced the cross-linking degree. The water resistance of polyurethane emulsion was further improved. Compared with PU without catechol group, the peel strength of leather substrate adhered by PDMAPU emulsion increased from 0.42 to 1.93 MPa, which indicated that PDMAPU has better bonding properties with leather. The bidentate hydrogen bond formed with catechol group as the reaction sites is considered to be the key reason for the adhesion of mussel-like polyurethane adhesive to hydrophilic substrates. This work provides an alternative to prepare environment-friendly high performance adhesive for hydrophilic substrates.     

邻苯二酚合成技术进展与市场分析

综合分析了国内邻苯二酚供需、生产和进出口等状况,对今后生产与消费趋势进行了预测。介绍了苯酚羟基化法技术进展,分析了我国与国外先进水平存在的差距,并提出了一些发展建议。     

Synthesis and characterization of poly(catechol) catalyzed by porphyrin and enzyme

Catalytic polymerization of catechol was performed employing the cationic porphyrin and horseradish peroxidase (HRP) as catalysts. The obtained results demonstrate that the cationic metalloporphyrin is a more-efficient catalyst than the HRP in the catechol polymerization. The oxidative polymerization was carried out in the presence of polystyrene sulfonate (PSS) as a template. According to TGA data, poly(catechol) that is synthesized by porphyrin catalyst exhibits more thermal stability than the enzymatic catalyzed product. The GPC indicate higher molecular weight of polymer synthesized by porphyrin as a catalyst. Cyclic voltammetry measurements show that the synthesized polymers have convenient electroactivity. The poly(catechol) and its methyl and methoxy derivatives that are synthesized by porphyrin catalyst show low electrical conductivity.     

乙基香兰素合成方法研究进展

介绍了乙基香兰素的性质、用途和生产状况,分别对原儿茶醛法、黄樟油素法、乙基愈创木酚法、对羟基苯甲醛法、对甲苯酚法、邻苯二酚法合成乙基香兰素的优劣进行了评述,并提出了以邻苯二酚为原料合成乙基香兰素的路线,展望了生物技术合成乙基香兰素的应用前景。