免费算命八字合婚

催化技术的开发与实施
详细工程和施工的作者监督
催化剂生产与供应
Supervision of catalysts charge and start-up operations
加氢脱蜡

催化脱蜡

免费算命八字合婚 参考信息

 

催化脱蜡工艺(加氢脱蜡)旨在改善低温下各种烃类进料的流动指数。用于降低润滑油和中间馏分的基本成分的倾点,柴油浊点和航空燃料的凝固点。这些特性决定了指定产品在低温下的行为。

在低温下,流动指数在很大程度上取决于石油成分和燃料中正构烷烃和接近正构烷烃的浓度。随着烃进料中石蜡浓度的升高,其倾点,浊点和凝固点增加。温度指数随着石蜡分子量(链长)的增加而下降。加氢脱蜡过程使用长链正构烷烃和接近正构烷烃的选择性裂解来改善这些指标。同时进行煤油和柴油燃料的深度加氢处理,去除硫和氮以及饱和芳族化合物。

加氢脱蜡工艺的主要特点如下:

  • 产品倾点低(-50以下)°C);
  • high stability of products;
  • good cetane properties of products;
  • constant quality of products during all cycle;
  • minimum viscosity decrease in comparison with other dewaxing processes;
  • 灵活性,允许在同一单元上生产石油成分和处理馏出物。

 

加氢脱蜡催化剂

在长链烷烃选择性加氢裂化的催化脱蜡工艺中,基于氧化铝或结晶铝硅酸盐的双功能催化剂,孔径为4-10 m-10 通常,该方法的第一阶段包括在烯烃饱和,脱硫和脱氮反应期间的进料加氢处理。预处理可保护催化剂并减少进料中有机硫和氮的含量,从而提高加氢裂化指数。

不同的公司开发了基于毛沸石,丝光沸石和ZSM-5的催化剂,它们被用于工业生产的喷气和柴油燃料。

In the USA Gulf Research and Devel Company created H-mordenit catalyst with 1% of palladium and 0,5% of titan content for hydrodewaxing of fuel oils, distillate fuel fractions, by means of which under the following process conditions:  temperature = 300 °C, pressure = 0.7 MPa, feed WHSV = 1.0 h-1, hydrogen circulation ratio = 1780 nm3/m3, - low-pour-point  fuels with pour point of minus  55 °C can be produced.

Texako Inс. developed dealuminated H-mordenit, used for oil straight-run distillates with pour point of 4-10°С to produce from them dewaxed gasoil with pour point of minus 18-60°С over the given catalyst under the following process conditions: temperature = 230-400°С, pressure = 1.4-10.5 МPа, feed WHSV= 0.25-5 h-1 . Hydrogen circulation ratio is 890-1800 nm3/m3.

For straight-run gasoil hydrodewaxing, distillated within the range of 204-400°С and having pour point of 9-13°С, Mobil Oil Со. developed Zn(Cd) catalyst ZSM-5 with 2 % content of palladium (platinum) and catalyst HZSM-5 with 0.5-5 % content of nickel, platinum, palladium, over which boiler fuel with pour point of minus 18°С (yield= 83-88 %) can be produced under the following process conditions: temperature = 307-371°С, pressure = 2.8-3.5 МPа, feed WHSV = 1-З h-1, hydrogen circulation ratio= 230-890 nm3/m3.

Depending on catalyst and initial feed, catalytic dewaxing process is carried out at temperature of 200-480 °C, pressure of 0.7 – 7.5 MPa, feed WHSV of 0.2-10 h-1, with H2/HC ratio = 178-1800 nm3/m3.  Nowadays the most effective catalysts in activity and operation stability are considered the ones based on zeolite of ZSM type, which almost completely superseded the catalysts based on erionite and mordenite.

在HZSM-5分子筛的基础上,美孚石油公司开发了催化剂及其催化脱蜡工艺  diesel fuel production from different types of feed under the common name “美孚馏分油脱蜡” (MDDW)。开发的催化剂可耐受硫和氮化合物的作用。催化剂不会除去硫和氮化合物,因此进料会受到加氢处理 before or after hydrodewaxing. Values of MDDW process parameters depend on requirements for target product quality, type of feed, its boiling range, viscosity, and change in the following ranges: pressure of 2.8-6.0 MPa, feed WHSV of 1-2 h-1, hydrogen supply = 200-440 nm3/m3 of feed. With decreasing catalyst activity, they rise temperature up to 400 °C for obtaining product with the required pour point. Then they carry out catalyst reactivation by hydrogen gas purging within 24 hours at temperature of 400-450 °C.

1974年首次在美孚法国炼油厂的加氢脱硫装置上进行了MDDW催化剂和工艺的工业检查。两次活化之间的间隔为10至60天。

Combined unit, including MDDW catalytic dewaxing and hydrotreatment [43], has been operating at SARNI Refinery of Gulf Oil company in Bertonico (Italy) since 1978. Capacity of the unit is 1910 m3 of gasoil per day.

1970年代开始开发用于低倾点柴油的家用馏分加氢处理催化剂。

In 1982 on the basis of TsVM VNIINP zeolite the first hydrodewaxing catalyst SGK-1 was developed and introduced into the industry in OJSC Angarsk Petrochemical Company (earlier – PO Angarsknefteorgsintez),可以从相应的加氢处理的煤油和一级或二级来源的柴油馏分生产高质量的低凝航空,柴油。 SGK-1催化剂包含12.5-27.7%的氧化铝,2.0-5.0%的氧化镁,氧化钙,氧化硼,0.9-15.1%的氢化组分和NTsVM沸石。在活性和选择性方面,SGK-1催化剂及其改性SGK-5不能令人满意,并且在某些参数上超过了这类最佳外来催化剂。

 

催化脱蜡工艺的工艺方案

下图显示了催化脱蜡工艺的简化标准方案。将新鲜饲料加热并与热循环气体混合。将混合物供应至第一反应器,在其中将氮和硫有机化合物转化为氨和硫化氢。反应以相对较低的热量释放进行。然后,预处理过的物流被来自压缩机的再循环气体冷却,并进料到包含脱蜡催化剂的第二反应器中。当进料通过脱蜡催化剂时,长链正构烷烃会分解成较小的分子,从而增加低温下的进料流动指数。反应是放热的,需要连续控制反应器温度。将温度保持在获得必要程度的分子分裂所需的最小可能水平。

反应器中的温度通过在催化剂床之间供应冷循环氢气来调节。来自第二个反应器的产物在进料热交换器中冷却,然后进料到高温高压(HP)分离器,在此处进行从氢气中分离出液态烃的过程。将液体产物引导至分馏区,将额外冷却后的氢气供入冷的HP分离器中。为了防止腐蚀和铵盐沉积,在将产品引导至冷却之前,需提供冲洗水。来自冷高压分离器的蒸汽与补充氢气混合,并直接与进料混合。将液态碳氢化合物送入低压(LP)分离器。

从LP分离器分离出的酸性气体从装置中分离出来,分离出酸性水后的液体产物被引导至分馏区。

加氢处理催化剂

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