丙烯腈装置节能降耗技术

简要分析了齐鲁石化公司4.0万吨/年丙烯腈装置的能耗组成,有针对性地开发应用了一系列节能降耗技术,具体为废水焚烧炉余热回收技术、废水浓缩技术、膜法富氧助燃技术、新型高效丙烯腈催化剂、提高丙烯腈精制回收率技术、硫胺逆流双效蒸发技术等。一系列技术实施后丙烯腈装置的能耗值由2000年的495.6 kg标油/t.AN降低到2010年的150 kg标油/t.AN,创本装置历史最好水平。     

中国丙烯腈生产技术国产化发展过程

论述了30年来中国丙烯腈生产技术的发展概况和目前达到的技术水平。中国于1960年开始氨氧化法制丙烯腈技术的开发,大致可分为三个时期:1960—1969年实验室基础研究和中间试验,进行了固定床和流化床及相适应的催化剂以及丙烯腈回收精制工艺的研究。1970—1980年建成了一批生产装置并进一步改善了生产工艺和催化剂。1981年到目前是以国际先进水平为目标,开发了高性能催化剂、流化床反应器和新的丙烯腈回收精制工艺。目前已开发成功的MB-86型催化剂、内构件流化床、复合萃取分离新工艺等具有国际80年代末期水平。丙烯单耗为1.02—1.05t丙烯/t丙烯腈,同时可分离出纤维级丙烯腈,高纯度氢氰酸和浓度达80%的乙腈。也完成了乙腈精制、硫铵回收等副产物回收技术。在此基础上已经开始设计两个万吨级丙烯腈工厂。     

UOP超低压连续重整技术工业应用与研究

UOP超低压连续重整技术以其较高的芳烃产率、较高的液体收率和氢气产率等特点，深受广大炼厂青睐。为进一步提升产品附加值、优化产品结构，某公司投资建设了100万t/a连续重整装置。通过对装置的全面标定可知，在装置原料与设计存在较大差别的情况下，预加氢单元超负荷、重整单元满负荷生产时，重整汽油辛烷值可以达到102.4以上，催化剂单耗为0.003 kg/t,装置标油能耗为98.63 kg/t,总体可以达到设计要求。但也存在诸如催化剂单耗偏高、部分单元设计不科学等问题，需进一步对装置进行消缺、改造，优化工艺操作参数。     

用PG型催化剂生产聚丙烯

在气相法聚丙烯装置上使用PG型催化剂生产聚丙烯1102K,并与装置原来使用的进口催化剂进行了比较,对比评价了催化剂配制情况、催化剂活性、催化剂单耗,对氢气的敏感性、熔体流动速率可调性、对原料适应性、聚丙烯粒径分布.结果表明:PG型催化剂的活性较高,达到23.736 5 kg/g(以.每克催化剂生产聚丙烯的质量计),比进口催化剂高40％;装置操作稳定,所产聚丙烯1102K树脂颗粒形态好,产品质量达到进口催化剂生产1102K树脂的水平.     

干法常温精脱硫技术在丙烯腈装置中的应用

由于原料丙烯中的硫化物COS、H2S、硫醇和硫醚等,极易造成丙烯腈催化剂中毒,严重影响催化剂的收率及寿命。齐鲁石化公司腈纶厂采用中国石油大学(北京)开发的常温干法精脱硫技术,对丙烯腈装置使用的原料丙烯进行脱硫精制,来确保丙烯质量满足丙烯腈装置的生产需求。项目投用后:装置运行稳定,脱硫后丙烯总硫小于1 g/m3,精制丙烯质量达到工艺包的技术要求。     

新品开发

上海石化研究院推出新型丙烯腈催化剂上海石化研究院最近推出了全新的SAC2000丙烯腈催化剂。该新型催化剂具有低反应温度、高催化剂负荷、高丙烯腈收率、环境保护更友好等特点。目前,该催化剂在高桥石化公司化工厂9000吨/年丙烯腈装置上进行了工业应用。结果表明,使用该催化剂,在反应温度430℃、反应压力0.14兆帕、催化剂负荷0.09的反应条件下,丙烯腈收率达到81%-82%,丙烯腈单耗1.04左右,(目前工业装置上普遍收率为78%-79%,丙烯腈单耗为1.1左右),在COD相同情况下,污水排放量减少20%。该催化剂的丙烯腈的收率优于目前市场上正在使用的国外…     

降低催化裂化装置催化剂单耗的措施

2013年,陕西延长石油（集团）炼化公司延安炼油厂为了大力推进装置节能降耗、挖潜增效工作,要求最大程度的降低能化剂单耗,指标为不大于0．80kg／t原料油,而2012年1.0Mt／a催化裂化装置催化剂单耗为0．85kg／t原料油。通过投用干气预提升及优化装置操作,2013年催化剂单耗降低到0．76kg／t原料油,达到了指标要求。     

技术改造降低丙烯单耗

分析了连续式双环管聚丙烯液相本体装置单耗高的原因,阐述了通过调整工艺参数和技术改造．降低了丙烯单耗。突破装置提升负荷的瓶颈,使丙烯单耗从开工初期的1097kg／t降至2008年的1026kg／t,取得了一定经济效益。     

信息与动态

上海石油化工研究院推出新型丙烯催化剂　　上海石油化工研究院最近推出全新SAC 2 0 0 0丙烯催化剂。该新型催化剂具有低反应温度、高催化剂负荷、高丙烯收率、环境保护更友好等特点。该催化剂已在高桥石化公司化工厂 9kt/a丙烯装置上进行了工业应用。结果表明 ,在温度 4 30℃、压力 0 14MPa、催化剂负荷 0 0 9的反应条件下 ,丙烯收率可达 81%～ 82 % ,丙烯单耗 1 0 4左右。而目前工业装置收率为 78%～ 79% ,丙烯单耗为 1 1左右。该催化剂的另一突出优点是在COD相同情况下 ,污水排放量减少 2 0 %。按高桥石化公司化工厂丙烯生产装置现…     

国产丙烯氨氧化催化剂创运行纪录

大庆石化公司化工二厂6万吨／年丙烯腈装置自首次应用上海石油化工研究院研制开发的MB-98丙烯氨氧化催化剂至今,已连续运行近7年,创造了国内丙烯腈催化剂连续运行的最长周期纪录。     

反应条件对SANC-08丙烯腈催化剂活性的影响

通过对反应工艺条件的研究,得出了SANC-08催化剂实验室的最佳工艺条件：反应温度（425～445） ℃,压力（0.082～0.14） MPa,n(空气)∶n(丙烯)=9.0～10.0、n(氨气)∶n(丙烯)=1.15～1.30、空速（0.060～0.090） h^-1。催化剂在较宽的工艺条件范围,具有丙烯腈收率高、氨转化率高、丙烯选择性好、反应温度低且可在低n(空气)∶n(丙烯)和高空速下运行等特点。     

Inhibition of Propylene Oxidation to Acrylic Acid by Amorphous Overlayers on MoV(Nb)TeO Based M2 Catalysts

One of the most effective catalysts for the selective oxidation of propane to acrylic acid (AA) and ammoxidation to acrylonitrile (AN) is the MoV(Nb,Ta)(Te,Sb)O system, comprised of two phases, with M1 the major catalyst and M2 the co-catalyst in symbiosis with M1, converting intermediately formed propylene to the respective desired end products. An improvement in either phase should enhance the overall desired yields of a combined M1/M2 conglomerate. The current study concentrates on the M2 phase (variously substituted and/or doped) where depending on composition and preparation technique crystalline materials or crystalline materials with amorphous overlayers are obtained. Crystalline M2 catalysts without amorphous overlayers are vastly superior to those encumbered with overlayers. In a comparative study the former give a maximum AN yield of ~45% in propylene ammoxidation, the latter ~24%. In the selective oxidation of propylene to acrylic acid, the difference in performance between the two types of catalysts becomes enormous: The crystalline M2 catalyst gives a maximum AA yield of ~34% while the Te–molybdate overlayered M2 a meager ~3%. Doping of crystalline M2 phase with P significantly enhances AA yields over the base and should be seriously considered in future attempts to improve M1/M2 propane/propylene catalyst systems.     

丙烯腈生产技术进展

概述了国内外丙烯氨氧化制丙烯腈生产技术进展和丙烷路线的开发情况以及市场供需状况。     

TRANSIENT RESPONSE ANALYSIS IN THE DETERMINATION OF ADSORPTION RATE COEFFICIENTS FOR PROPYLENE AND NITRIC OXIDE ON NiO/Al203 AEROGEL CATALYSTS

Nickel oxide on alumina aerogel catalysts are known to be active and selective for the formation of acrylonitrile from nitric oxide and propylene. During an effort to investigate the mechanism of this reaction some transient feed experiments were carried out. The results obtained from these transient experiments were used to calculate the adsorption coefficients of propylene and nitric oxide on a NiO/Al₂O₃ aerogel catalysts with 1:1 Ni to Al atomic ratio. Adsorption coefficients of nitric oxide and propylene was determined by independently flowing the respective gases over the catalyst in a stream of helium at 410° C. Adsorption coefficient of nitric oxide on the catalyst at an oxidized state has been found to be less than that of propylene. When the two reactant gases flowed across the catalyst together the rate of adsorption of nitric oxide increased as the catalyst was reduced by propylene adsorption. The increased rate of adsorption of nitric oxide does not, however, influence the overall rate of formation of acrylonitrile.     

Doping of MoVNbTeO (M1) and MoVTeO (M2) Phases for Selective Oxidation of Propane and Propylene to Acrylic Acid

The effectiveness of MoV(Nb,Ta)(Te,Sb)O catalysts for the selective oxidation of propane to acrylic acid (AA) and ammoxidation to acrylonitrile (AN) is well known and recorded in the literature. One of the best known catalyst systems is comprised of two phases: M1 (orthorhombic) Mo_7.8V_1.2NbTe_0.94O_28.9 and M2 (pseudo-hexagonal) Mo_4.67V_1.33Te_1.82O_19.82, usually in a 60/40 ratio. The M1 structure performs all of the catalytic functions needed for converting propane to acrylic acid or acrylonitrile, since all key metals having the desired catalytic functions are located at the active center of the catalyst and within bonding distance of each other to perform this complex task. The M2 phase is a co-catalyst in symbiosis with M1, performing a mop-up operation converting free intermediately formed propylene to the respective desired end products (AA or AN). Various attempts have been reported in the literature, with varying degrees of success, to substitute select elements of the two respective structures to enhance the yields of the desired end products. A yield improvement in either phase should theoretically lead to an enhancement of the overall desired yield and of M1/M2 optimal mixtures. Our current study concentrates on the selective doping of the M1, as well as, M2 structure in the selective oxidation of propane and propylene, respectively, to acrylic acid; it centers at doping these structures with low levels of elements having acidic (P, B, W) or redox (Cu) properties. Higher acrylic acid yields were obtained with the doped M1 (2–5%) and M2 (up to 15%) systems. Directed, high throughput methodology was employed as the experimental technique. The study of low doping levels is being extended to include a broader base of elements, as well as, M1/M2 mixtures (optimum compositions) aimed at achieving still higher useful product yields (AA or AN).     

TRANSIENT RESPONSE ANALYSIS IN THE DETERMINATION OF ADSORPTION RATE COEFFICIENTS FOR PROPYLENE AND NITRIC OXIDE ON NiO/Al203 AEROGEL CATALYSTS

Nickel oxide on alumina aerogel catalysts are known to be active and selective for the formation of acrylonitrile from nitric oxide and propylene. During an effort to investigate the mechanism of this reaction some transient feed experiments were carried out. The results obtained from these transient experiments were used to calculate the adsorption coefficients of propylene and nitric oxide on a NiO/Al₂O₃ aerogel catalysts with 1:1 Ni to Al atomic ratio. Adsorption coefficients of nitric oxide and propylene was determined by independently flowing the respective gases over the catalyst in a stream of helium at 410° C. Adsorption coefficient of nitric oxide on the catalyst at an oxidized state has been found to be less than that of propylene. When the two reactant gases flowed across the catalyst together the rate of adsorption of nitric oxide increased as the catalyst was reduced by propylene adsorption. The increased rate of adsorption of nitric oxide does not, however, influence the overall rate of formation of acrylonitrile.     

氧浓度强制振荡下的丙烯氨氧化反应过程

<正>自从70年代初有学者对催化反应过程的强制振荡操作进行实验研究以来,人们已越来越注意到,对于某些催化反应过程,采用合适的强制周期振荡操作条件比相应的稳态操作产生更优的反应效果,尤其是一些催化氧化反应过程,国内外已有许多研究者开展了大量的实验研究,发现在一定强制振荡周期及振幅操作下能显著提高反应速率（转化率）、主产物的选择性及收率。同时,有许多周期性反应体系的数学模拟理论研究也表明强制振荡操作能     

SANC-08丙烯腈合成催化剂的开发

实验室开发出新型SANC-08丙烯腈合成催化剂,在反应温度440 ℃、反应压力0.084 MPa、催化剂负荷0.06 h^-1、n(空气)∶n(丙烯)=9.5和n(氨气)∶n(丙烯)=1.25反应条件下,丙烯转化率97%以上,丙烯腈选择性82%以上,丙烯腈收率大于80%,氨转化率94%以上。流化床反应器稳定性试验结果表明, 2 177 h时,丙烯腈收率78.9%,丙烯转化率94.6%,丙烯腈选择性83.3%。