EP1583606A1 - Verfahren zur herstellung von hochoktanbenzin aus direktdestilliertem leichtem naphta mit einem platinenthaltenden hzsm-5 molekularsiebkatalysator - Google Patents

Verfahren zur herstellung von hochoktanbenzin aus direktdestilliertem leichtem naphta mit einem platinenthaltenden hzsm-5 molekularsiebkatalysator

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Publication number
EP1583606A1
EP1583606A1 EP02781717A EP02781717A EP1583606A1 EP 1583606 A1 EP1583606 A1 EP 1583606A1 EP 02781717 A EP02781717 A EP 02781717A EP 02781717 A EP02781717 A EP 02781717A EP 1583606 A1 EP1583606 A1 EP 1583606A1
Authority
EP
European Patent Office
Prior art keywords
light naphtha
range
temperature
bed
zeolite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02781717A
Other languages
English (en)
French (fr)
Inventor
Perupogu Indian Inst. of Petroleum VIJAYANAND
Surinder Mohan Indian Inst. of Petroleum DHIR
Lalji Indian Institute of Petroleum DIXIT
Sneh Indian Institute of Petroleum CHOPRA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Council of Scientific and Industrial Research CSIR
Original Assignee
Council of Scientific and Industrial Research CSIR
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Council of Scientific and Industrial Research CSIR filed Critical Council of Scientific and Industrial Research CSIR
Priority claimed from PCT/IB2002/005644 external-priority patent/WO2004058400A1/en
Publication of EP1583606A1 publication Critical patent/EP1583606A1/de
Withdrawn legal-status Critical Current

Links

Definitions

  • the present invention relates to a process for the production of high-octane gasoline from straight run light naphtha on Pt containing HZSM-5 molecular sieve catalyst. More particularly the present invention relates to a process for the utilization of straight run light naphtha feedstock available from various refineries, into value added aromatics with low amounts of benzene which can be used as blending stocks for improvement of octane number in gasoline fuel. In addition to high-octane gasoline liquid product, some amounts of gas byproduct are also obtained which can be used as domestic fuel (LPG).
  • LPG domestic fuel
  • Light naphtha mainly contains C 5 and C 6 hydrocarbons (30 to 40 wt%) depending upon the source. Due to high percentage of n-paraffins in light naphtha it has lower research octane number (RON) and high RVP (Reid Vapour Pressure) due to n- and i-pentanes, hence it cannot be used directly for gasoline blending. Thus, the conversion of light naphtha into other petroleum and petrochemical products gains significance in this scenario.
  • gasoline is being produced from the Catalytic reforming process of naphtha and Fluid catalytic cracking units from various refineries.
  • the indigenous gasoline production by refineries with low benzene content will be inadequate to meet the demands in future like at present.
  • the catalyst used for reforming process is monometallic Pt/Al 2 O 3 or Pt- Re/Al 2 O 3 bimetallic catalyst.
  • the conventional catalyst is not effective in promoting aromatization of light naphtha rich in Cs hydrocarbons.
  • the catalyst is also not very effective in promoting the aromatization of straight chain paraffins such as n-hexane and n-heptane present in the feed that remain unconverted.
  • LPG production either from refineries or from gas fields is not enough to meet the demands.
  • the import situation is also not encouraging, as only a few private entrepreneurs have actually created facilities for import market. Therefore the increasing demand for good quality gasoline and increasing gap between LPG deficit and import capacity also indicates the need to develop novel processes for the production of gasoline as well as LPG from cheaply available feed stocks, viz., light naphtha.
  • ZSM-5 catalyst for the production of mono-alkyl aromatics from C 8 n-paraffins containing feed stocks has been described.
  • the limitation of the above process is production of xylenes from C ⁇ -C ⁇ hydrocarbons.
  • NNL natural gas liquid
  • LPG liquefied petroleum gas
  • high-octane gasoline high-octane gasoline over modified ZSM-5 zeolite
  • the limitation of above process is that zeolite catalyst was modified by steaming method and it produces more LPG (55 wt%) than aromatics (22wt%).
  • the main object of the invention is to provide a process for the production of high- octane gasoline from straight run light naphtha on platinum containing HZSM-5 molecular sieve catalyst, which obviates the drawbacks as detailed above.
  • Another object of the invention is to provide a process for the conversion of light naphtha into high octane low benzene content unleaded gasoline as a blender to boost the octane number along with LPG as by product by using a catalyst system containing platinum supported ZSM-5 zeolite composite.
  • Another object of the present invention is to provide a process for the preparation of platinum metal modified ZSM-5 zeolite catalyst by impregnation method with out acidity modification by steaming and acid leaching steps.
  • Another object of invention is to provide a process that produces in addition to n- paraffinic and naphthenic components, isoparaffins; benzene and other aromatics present in the feed also can be effectively converted to give high octane gasoline with low benzene content and LPG.
  • the present invention provides a process for the production of high- octane gasoline from straight run light naphtha over a Pt containing HZSM-5 molecular sieve catalyst which comprises i) impregnating 0.1-2.0 wt% of Pt from tetramine platinum chloride on a HZSM-5 zeolite extrudate, ii) drying the zeolite extrudate followed by calcination, iii) loading the Pt impregnated zeolite extrudate in a high pressure reactor and reducing it iv) cooling the Pt impregnated zeolite bed and then increasing the bed temperature v) passing light naphtha through the bed to obtain a mixture of high octane gasoline and
  • step (ii) the zeolite extrudate is dried at a temperature of about 110°C and for a period of 10-12 hrs and then calcined at a temperature in the range of 400-600°C for a period of 1 -4 hrs in static air.
  • the treated Pt impregnating zeolite extrudate is reduced inside the high pressure reactor in step (iii) by passing hydrogen for a period in the range of 2-5 hours at a temperature in the range of 400-500°C and at a flow rate in the range of 8-12 1/h into the reactor.
  • the Pt impregnated zeolite bed is first cooled to a temperature of about 300°C under nitrogen atmosphere and the bed temperature thereafter increased to a range of 300-600°C.
  • step (v) of the process light naphtha is passed through the bed at a weight hourly space velocity in the range of 1 to 8 hrs "1 and at a pressure in the range of 1 to 25 kg/cm 2 and in the absence of nitrogen.
  • the light naphtha feedstock comprises light naphtha containing C 6 to C 8 range paraffins and naphthenes.
  • reaction temperature is in the range of 400-500°C.
  • pressure is in the range of 1-10 kg/cm 2 .
  • the weight hourly space velocity of light naphta is in the range of 2-8hrs " ⁇
  • the Research Octane Number (RON) of straight light naphtha fraction is increased from 64 to 97 in the product with gain of 34 units.
  • the platinum impregnated ZSM- 5 zeolite composite used is prepared by incipient wetness method.
  • the catalyst used is regenerated by oxidative combustion.
  • the total amount of platinum metal added into HZSM-5 molecular sieve is in the range of 0.1 to 1.1 wt%.
  • the catalyst used results in the reduction of the sulfur content in light naphtha feed stock from 50 ppm level sulfur to 10 ppm level sulfur in the obtained product.
  • the pressure is varied to in order to increase the aromatic content and decrease the LPG in product mixture.
  • preparation of the catalyst for the process does not involve the steps of steaming and acid leaching before the actual catalytic application.
  • the mentioned catalyst is environmentally friendly as the preparation does not involve the use of hazardous mineral acids, viz., HC1, HNO 3 etc.
  • the detailed steps of the process are:
  • Regeneration of the deactivated catalyst in reactor is carried out by conventional procedure using air and nitrogen mixture.
  • the liquid product is analyzed using a gas Chromatograph fitted with Tetra Cyano Ethoxy Propionitrile column and FID detector.
  • the gaseous products are analyzed using Squalane column.
  • the process conditions controls the C ⁇ + C 2 (dry gas) yield, which is not desired in the gasoline process.
  • 0.4 wt% of platinum metal is doped on HZSM-5 catalyst.
  • the process can operate for maximization of LPG as well by simply altering process parameters.
  • the catalyst used in present process is a novel platinum supported HZSM-5 zeolite in which parent ZSM-5 zeolite composite was procured from Zeolyst international (Lot No. 1822-43).
  • the zeolite to binder ratio of HZSM-5 extrudates was 80:20. These extrudates were impregnated with 0.4 wt% of Pt from tetraamine platinum chloride (Aldrich) solution. These extrudates were oven dried at 110°C for 12 hrs and then processed to calcination at 500°C for 3hrs in static air.
  • the Physico-chemical properties of the zeolite catalyst are as follows:
  • This example describes the characteristics of the high-octane gasoline liquid product and LPG obtained in the present process from light naphtha feed stock. Yields of individual product components that are obtained are given. Analysis is based on GC fitted with Tetra Cyano Ethoxy Propionitrate column and FID detector. Table - 1: Characteristics of Feed and Liquid Products of this process Process conditions: Catalyst: Pt/HZSM-5; Feed: light naphtha of Numaligharh refinery; -Reaction Temperature: 450°C; Pressure: 3kg/cm 2 ; WHSV: ⁇ hr "1 ; TOS: 24 hrs; Reactor: Micro Reactor of 25 gm-catalyst capacity.
  • Table 1 shows conversion of light naphtha feed stock having RON of 64 into aromatics rich (60%) liquid product with low benzene content having RON 97.4. 85 wt% of high-octane gasoline was produced from low value feedstock, which also met environmental regulations on gasoline in terms of low benzene content and low sulphur level.
  • EXAMPLE - 2 shows conversion of light naphtha feed stock having RON of 64 into aromatics rich (60%) liquid product with low benzene content having RON 97.4. 85 wt% of high-octane gasoline was produced from low value feedstock, which also met environmental regulations on gasoline in terms of low benzene content and low sulphur level.
  • Table-2 shows that yield of aromatics (BTX) increases with increase of temperature and optimum temperature for the present process was chosen as 450°C due to formation of less coke during reaction.
  • EXAMPLE - 3 This example includes results of effect of pressure on yields and composition of aromatics and LPG. The product analysis is presented in table-3. Table - 3: Effect of Pressure on Product Yields
  • EXAMPLE - 4 This example illustrates effect of weight hourly space velocity on yield and composition of high-octane gasoline and LPG.
  • Table - 4 Effect of Weight Hourly Space Velocity on Product Yields Process conditions: Catalyst: Pt/HZSM-5; Feed: Straight run light naphtha; Temperature: 450° C; Pressure: 3 kg/cm 2 ; TOS: 24 hrs
  • Table-6 shows the similar yield patterns of BTX aromatics in liquid product and LPG in both before and after the regeneration of the catalyst indicating the complete removal of coke lay down during the reaction.
  • the main advantages of the present invention are: l.
  • the process of the present invention converts all types of hydrocarbon components present in the light naphtha feed viz. Paraffins, isoparaffins, naphthenes and benzene into aromatic hydrocarbons, isoparaffinic and LPG, at high selectivity with single catalyst system.
  • 2.Light naphtha which does not have potential use as conventional reformer feed stock, can be used as a feed in this process.
  • the catalyst used in this process is ecofriendly and it does not involve acid leaching with hazardous mineral acids such as HC1 during preparation.
  • the catalyst used in this process reduces dry gas yields to 2 wt% with increase of high- octane liquid product and thereby improves the economics of this process.
  • LPG which is a by-product in the present process, can meet the industrial and domestic demands. 6. The process does not require hydrogen during feed cut in.
  • the high-octane liquid a major product obtained in the process can be used as a gasoline blender to boost octane number.
  • 9.This process is economically profitable and depending on the capital investment the pay back period will be 1.5 to 3 years. lO. The process maintains constant production of high-octane gasoline pool by utilization of light naphtha from reformate.
  • the catalyst can desulphurize the synthesized gasoline to lOppm from 50ppm of light naphtha feed.

Landscapes

  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
EP02781717A 2002-12-27 2002-12-27 Verfahren zur herstellung von hochoktanbenzin aus direktdestilliertem leichtem naphta mit einem platinenthaltenden hzsm-5 molekularsiebkatalysator Withdrawn EP1583606A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2002/005644 WO2004058400A1 (en) 2002-12-27 2002-12-27 PROCESS FOR PRODUCTION OF HIGH OCTANE GASOLINE FROM STRAIGHT RUN LIGHT NAPHTHA ON Pt CONTAINING HZSM - 5 MOLECULAR SIEVE CATALYST

Publications (1)

Publication Number Publication Date
EP1583606A1 true EP1583606A1 (de) 2005-10-12

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EP02781717A Withdrawn EP1583606A1 (de) 2002-12-27 2002-12-27 Verfahren zur herstellung von hochoktanbenzin aus direktdestilliertem leichtem naphta mit einem platinenthaltenden hzsm-5 molekularsiebkatalysator

Country Status (3)

Country Link
EP (1) EP1583606A1 (de)
JP (1) JP2006512437A (de)
AU (1) AU2002348688A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114806651A (zh) * 2022-05-12 2022-07-29 陈记 一种改性醇基复合环保燃料

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5378774B2 (ja) * 2008-11-28 2013-12-25 Ｊｘ日鉱日石エネルギー株式会社 改質器付き火花点火エンジン用燃料油組成物
CN112939015A (zh) * 2021-01-21 2021-06-11 山东京博石油化工有限公司 一种分子筛、芳构化催化剂及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004058400A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114806651A (zh) * 2022-05-12 2022-07-29 陈记 一种改性醇基复合环保燃料
CN114806651B (zh) * 2022-05-12 2023-07-14 陈记 一种改性醇基复合环保燃料

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AU2002348688A1 (en) 2004-07-22
JP2006512437A (ja) 2006-04-13

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