Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
  • C10G11/04—Oxides
  • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves

Definitions

• the present invention relates to a process for the conversion of a hydrocarbonaceous feedstock.
• the present invention provides a process for the conversion of a hydrocarbonaceous feedstock having an end boiling point of at most 330 °C, which process comprises contacting the feed­stock with a zeolitic catalyst comprising a zeolite with a pore diameter of 0.3 to 0.7 nm, preferably 0.5 to 0.7 nm, at a temperature above 500 °C during less than 10 seconds.
• the feedstock is contacted with the zeolitic catalyst for less than 10 seconds.
• the minimum contact time is 0.1 second. Very good results are obtainable with a process in which the feedstock is contacted with the zeolitic catalyst during 0.2 to 6 seconds.
• US-A-4,100,2108 describes a process for the preparation of LPG (saturated C3 ⁇ 4-hydrocarbons) and gasoline starting from an olefinic stream, using a catalyst with a pore diameter of less than 0.7 nm. Since it was known that such zeolitic catalysts have activity to catalyze the conversion of olefins to saturated and aromatic hydro­carbons, it is surprising that in the present process olefins are produced and relatively little saturated gaseous hydrocarbon product is formed.
• the temperature during the reaction is above 500 °C and preferably up to 900 °C.
• the temperature is preferably from 550 to 800 °C.
• the zeolitic catalyst may comprise one or more zeolites with a pore diameter of from 0.3 to 0.7 nm.
• the catalyst suitably further comprises a refractory oxide that serves as binder material. Suitable refractory oxides include alumina, silica, silica-­alumina, magnesia, titania, zirconia and mixtures thereof. Alumina is especially preferred.
• the weight ratio of refractory oxide and zeolite suitably ranges from 10:90 to 90:10, preferably from 50:50 to 85:15.
• the zeolitic catalyst preferably comprises as zeolite substantially only zeolites with a pore diameter of from 0.3 to 0.7 nm. Illustrative of the invention is the use of a zeolitic catalyst comprising a zeolite of pore diameter of 0.5 to 0.7 nm at a temperature above 500 °C and up to 750 °C.
• zeolite in this specification is not to be regarded to comprise only crystalline aluminium silicates.
• the term also includes crystalline silica (silicalite), silicoaluminophosphates (SAPO), chromo­silicates, gallium silicates, iron silicates, aluminium phosphates (ALPO), titanium aluminosilicates (TASO), boron silicates, titanium aluminophosphates (TAPO) and iron aluminosilicates.
• Examples of zeolites that may be used in the process of the invention and that have a pore diameter of 0.3 to 0.7 nm include SAPO-4 and SAPO-11, which are described in US-A-4,440,871, ALPO-11, described in US-A-4,310,440, TAPO-11, described in US-A-4,500,651, TASO-45, described in EP-A-229,295, boron silicates, described in e.g. US-A-4,254,297, aluminium silicates like erionite, ferrierite, theta and the ZSM-type zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-23, and ZSM-38.
• SAPO-4 and SAPO-11 which are described in US-A-4,440,871, ALPO-11, described in US-A-4,310,440, TAPO-11, described in US-A-4,500,651, TASO-45, described in EP-A-229,29
• the zeolite is selected from the group consisting of crystalline metal silicates having a ZSM-5 structure, ferrierite, erionite and mixtures thereof.
• crystalline metal silicates with ZSM-5 structure are aluminium, gallium, iron, scandium, rhodium and/or chromium silicates as described in e.g. GB-B-2,110,559.
• an amount of alkali metal oxide is present in the readily prepared zeolite.
• the amount of alkali metal is removed by methods known in the art, such as ion exchange, optionally followed by calcination, to yield the zeolite in its hydrogen form.
• the zeolite used in the present process is substantially in its hydrogen form.
• the pressure in the present process can be varied within wide ranges. It is, however, preferred that the pressure is such that at the prevailing temperature the feedstock is substantially in its gaseous phase or brought thereinto by contact with the catalyst. Then it is easier to achieve the short contact times envisaged. Hence, the pressure is preferably relatively low. This can be advantageous since no expensive compressors and high-pressure vessels and other equipment is necessary. A suitable pressure range is from 1 to 10 bar. Sub­atmospheric pressures are possible, but not preferred. It can be economically advantageous to operate at atmospheric pressure. Other gaseous materials may be present during the conversion such as steam and/or nitrogen.
• the present process is preferably carried out in a moving bed.
• the bed of catalyst may move upwards or downwards. When the bed moves upwards a process some­what similar to a fluidized catalytic cracking process is obtained.
• the catalyst is regenerated by subjecting it after having been contact­ed with the feedstock to a treatment with an oxidizing gas, such as air.
• a continuous regeneration similar to the regeneration carried out in a fluidized catalytic cracking process, is especially preferred.
• the residence time of the catalyst particles in a reaction zone is longer than the residence time of the feedstock in the reaction zone.
• the contact time between feedstock and catalyst should be less than 10 seconds.
• the contact time generally corresponds with the residence time of the feedstock.
• the residence time of the catalyst is from 1 to 20 times the residence time of the feedstock.
• the catalyst/feedstock weight ratio is not critical, it is preferred that the weight ratio varies from 1 to 150 kg or more of catalyst per kg of feed­stock. Preferably, the catalyst/feedstock weight ratio is from 20 to 120:1.
• the feedstock which is to be converted in the present process comprises hydrocarbons which have an end boiling point of at most 330°C.
• hydrocarbons which have an end boiling point of at most 330°C.
• relatively light petroleum fractions like naphtha and kerosine, are included.
• the feedstock has an initial boiling point of -45 °C.
• Suitable feedstocks include C3 ⁇ 4-hydrocarbons (e.g. LPG), naphtha, gasoline fractions, kerosine fractions and mixtures thereof.
• a feedstock with a relatively high nitrogen content may be used with substantially no effect on the catalyst activity.
• Suitable feedstocks may have a nitrogen content of more than 25 ppmw, calculated as nitrogen.
• the feedstock may even have a nitrogen content of 100 to 1000 ppmw, calculated as nitrogen.
• the experiments were carried out in a down flow reactor in which co-currently a flow of feedstock and catalyst particles, having an average particle size of 74 micrometers, was passed downwards.
• the catalyst used comprised ZSM-5 in hydrogen form in an alumina matrix (weight ratio ZSM-5/alumina was 1:3). All experiments were carried out at atmospheric pressure. Further process conditions and the results of the experiments are indicated in Table 1 below.
• n-paraffins are preferentially cracked and yield gaseous products which comprise a significant amount of olefins, especially at temperatures above 500 °C. Above 500 °C it will be seen that there is a markedly increased C3 and C4 olefin/paraffin ratio and an overall increased conversion to lower olefins.
• the resulting liquid product has a higher iso/normal-paraffin ratio than the starting mixture, so that, additionally, the octane number and hence the quality of the liquid product as a gasoline has been enhanced.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Crystallography & Structural Chemistry (AREA)
• Catalysts (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (4)

Publications (2)

Family

ID=26294030

Family Applications (1)

Country Status (10)

Cited By (12)

Families Citing this family (9)

Citations (7)

Family Cites Families (1)

• 1989
  • 1989-06-14 BR BR898902859A patent/BR8902859A/pt not_active IP Right Cessation
  • 1989-06-14 KR KR1019890008211A patent/KR910001002A/ko not_active Withdrawn
  • 1989-06-14 ES ES89201558T patent/ES2087073T3/es not_active Expired - Lifetime
  • 1989-06-14 JP JP1149783A patent/JPH0245593A/ja active Pending
  • 1989-06-14 RU SU894614344A patent/RU2002794C1/ru active
  • 1989-06-14 DE DE68926408T patent/DE68926408T2/de not_active Revoked
  • 1989-06-14 EP EP89201558A patent/EP0347003B1/de not_active Revoked
  • 1989-06-14 PH PH38786A patent/PH25773A/en unknown
  • 1989-06-14 AU AU36394/89A patent/AU614626B2/en not_active Ceased
  • 1989-06-14 CN CN89104264A patent/CN1021913C/zh not_active Expired - Fee Related

Patent Citations (7)

Also Published As

Similar Documents

Legal Events