US20040149629A1 - Process for the preparation of and composition of a feedstock usable for the preparation of lower olefins - Google Patents

Process for the preparation of and composition of a feedstock usable for the preparation of lower olefins Download PDF

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Publication number
US20040149629A1
US20040149629A1 US10/358,129 US35812903A US2004149629A1 US 20040149629 A1 US20040149629 A1 US 20040149629A1 US 35812903 A US35812903 A US 35812903A US 2004149629 A1 US2004149629 A1 US 2004149629A1
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Prior art keywords
fraction
hydrocarbon feed
boiling point
synthetic
naphtha
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Abandoned
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US10/358,129
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English (en)
Inventor
Luis Dancuart Kohler
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Sasol Technology Pty Ltd
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Sasol Technology Pty Ltd
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Priority to US10/358,129 priority Critical patent/US20040149629A1/en
Assigned to SASOL TECHNOLOGY (PTY) LTD. reassignment SASOL TECHNOLOGY (PTY) LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KOHLER, LUIS PABLO DANCUART
Priority to BR0407158-1A priority patent/BRPI0407158A/pt
Priority to JP2006503927A priority patent/JP4543033B2/ja
Priority to GB0515611A priority patent/GB2412921B/en
Priority to ES200550048A priority patent/ES2279717B1/es
Priority to CN200710089556.2A priority patent/CN101033408A/zh
Priority to AU2004207852A priority patent/AU2004207852B2/en
Priority to PCT/ZA2004/000012 priority patent/WO2004067486A2/en
Priority to CN200480005586.5A priority patent/CN1756828B/zh
Publication of US20040149629A1 publication Critical patent/US20040149629A1/en
Priority to ZA200505976A priority patent/ZA200505976B/en
Priority to US11/707,366 priority patent/US20070203386A1/en
Abandoned legal-status Critical Current

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    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Definitions

  • the invention relates to a process for the preparation of lower olefins and a composition of a high performance feedstock usable in a process for the preparation of lower olefins from a hydrocarbon containing feed including at least a fraction boiling above the boiling point range of the lower olefins.
  • this feedstock can be used advantageously when the lower olefins process objective is propylene.
  • the thermal cracking process for production of lower olefins is the most important commercial route for the production of ethylene, propylene and other lower olefins from a hydrocarbon containing feed including at least a fraction above the boiling point range of the lower olefins.
  • the thermal cracking of naphtha feedstocks proceeds in two stages.
  • the primary reactions that take place in the first stage include the thermal decomposition of the reactants by free-radical chain mechanism into hydrogen, methane, ethylene, propylene, butylenes and higher olefins.
  • the second stage involves three types of reactions:
  • FT Fischer-Tropsch
  • FT reactors FT products
  • the FT process is a well known process in which carbon monoxide and hydrogen are reacted over an iron, cobalt, nickel or ruthenium containing catalyst to produce a mixture of straight and branched chain hydrocarbons ranging from methane to waxes and smaller amounts of oxygenates.
  • the FT process is used industrially to convert synthesis gas, which might derived from coal, natural gas, biomass or heavy oil streams, into hydrocarbons ranging from methane to species with molecular masses above 1400.
  • the main products are linear paraffinic materials
  • other species such as branched paraffins, olefins and oxygenated components may form part of the product slate.
  • the exact product slate depends on reactor configuration, operating conditions and the catalyst that is employed, as is evident from articles such as Catal.Rev.-Sci. Eng., 23(1&2), 265-278 (1981).
  • Preferred reactors for the production of heavier hydrocarbons are slurry bed or tubular fixed bed reactors, while operating conditions are preferably in the range of 160-280° C., in some cases in the 210-260° C. range, and 18-50 bar, in some cases preferably between 20-30 bar.
  • the catalyst may comprise active metals such as iron, cobalt, nickel or ruthenium. While each catalyst will give its own unique product slate, in all cases the product slate contains some waxy, highly paraffinic material which needs to be further upgraded into usable products.
  • the FT products can be hydroconverted into a range of final products, such as middle distillates, naphtha, solvents, lube oil bases, etc. Such hydroconversion, which usually consists of a range of processes such as hydrocracking, hydrotreatment and distillation, can be termed a FT products work-up process.
  • the invention provides a process for the preparation of lower olefins from a synthetic hydrocarbon feed including at least a fraction having a boiling point above the boiling point range of the lower olefins, wherein the hydrocarbon feed includes an unhydrogenated fraction, which process includes the thermal processing of the hydrocarbon feed.
  • the thermal processing may be thermal cracking of the synthetic hydrocarbon feed under thermal cracking conditions selected to suit the synthetic hydrocarbon feed composition.
  • the thermal cracking conditions are a temperature of from 400° C. to 1200° C., usually from 700° C. to 950° C. and at a pressure of from 0.1 to 20 bar absolute pressure, typically from 1 to 5 bar.
  • the residence time in a thermal cracking unit in which the thermal cracking is taking place may be from 50 ms to 1000 ms, or even longer. Typically the residence time may be below 300 ms. The residence time will however depend on the configuration of the thermal cracking unit used.
  • the thermal cracking may be carried out in the presence of an inert media.
  • This inert media might be steam or nitrogen.
  • the synthetic hydrocarbon feed may be the product of a FT reaction.
  • the synthetic hydrocarbon feed may be the processed product of the FT reaction.
  • the unhydrogenated fraction of the synthetic hydrocarbon feed may be an unhydrogenated fraction of the process products of the FT reaction.
  • the synthetic hydrocarbon feed may be prepared by combining at least
  • an unhydrogenated fraction of the process products of the FT reaction also referred to as an unhydrogenated FT fraction
  • a hydroconverted fraction of the process products of the FT reaction also referred to as a hydroprocessed or hydrocracked FT fraction.
  • the unhydrogenated FT fraction may include a fraction of the condensate product of the FT reaction.
  • the FT condensate is typically obtained as the liquid hydrocarbon stream from the FT products excluding the FT wax from a FT reactor in which the FT reaction has taken place.
  • the hydroprocessed FT fraction may be a hydrocracked FT wax fraction of the FT reaction products.
  • the FT wax fraction is typically obtained as the heavy hydrocarbons stream.
  • the invention extends to a hydrocarbon feed to a cracking process for the preparation of lower olefins from a synthetic hydrocarbon feed including at least a fraction having a boiling point above the boiling point range of the lower olefins, said hydrocarbon feed including at least a fraction which is unhydrogenated.
  • the synthetic hydrocarbon feed may be the product of a FT reaction.
  • the synthetic hydrocarbon feed may be the processed product of the FT reaction.
  • the synthetic hydrocarbon feed is optimised when the target product of the cracking process is propylene. Moreover, it has also been found that this synthetic hydrocarbon feed can yield significantly lower yields of the undesirable liquid product (C5+fraction) that is co-produced during cracking to lower olefins.
  • This synthetic hydrocarbon feed also referred to as olefinic naphtha, also has a low aromatics content, typically below 1% mass, preferably below 0.5% mass. This is believed to be a contributing factor to the superior thermal cracking performance.
  • the invention extends to a hydrocarbon feed to a cracking process for the preparation of lower olefins from a synthetic hydrocarbon feed including at least a fraction having a boiling point above the boiling point range of the lower olefins, said hydrocarbon feed comprising at least 15% olefins and at most 1.0% aromatics.
  • the hydrocarbon feed may comprise at least about 20% olefins.
  • a process for the preparation of a synthetic hydrocarbon feed to a process for producing lower olefins said feed including at least a fraction having a boiling point above the boiling point range of the lower olefins, said process including the steps of:
  • step b) fractionating the hydroconverted wax product from step b) to obtain a hydroconverted naphtha fraction separated from the other products from the hydroconversion process;
  • step d) blending said olefinic naphtha from step a) with the hydroconverted naphtha from step c) to obtain a synthetic hydrocarbon feed in a desired ratio having a boiling point above the boiling point range of the lower olefins.
  • the wax fraction of step b) may have a true boiling point (TBP) in the range of about 70° C. to 700° C., typically in the range 80° C. to 650° C.
  • TBP true boiling point
  • the FT condensate fraction of step a) may have a true boiling point (TBP) in the range ⁇ 70° C. to 350° C., typically ⁇ 10° C. to 340° C., usually ⁇ 70° C. to 350° C.
  • TBP true boiling point
  • step c) is blended with the synthetic hydrocarbon fraction of step a) in a volumetric ratio of from 1:4 to 4:1 to form the synthetic hydrocarbon feed of step d).
  • this volumetric ratio is 1:2 to 2:1, even more typically between 3:2 and 2:3.
  • a process for the preparation of a synthetic hydrocarbon feed for a process for producing lower olefins said feed including at least a fraction having a boiling point above the boiling point range of the lower olefins, said process including the steps of:
  • step b) blending said hydroconverted product from step a) with a straight run unhydrogenated condensate fraction in a desired ratio to obtain a blend that includes hydrocarbons boiling over a broad temperature range;
  • step c) fractionating the hydrocarbons blend from step b) to obtain a synthetic hydrocarbon feed for the thermal cracking process having a boiling point above the boiling point range of the lower olefins.
  • the hydroconverted product of step a) may be blended with the condensate hydrocarbon fraction in step b) in a volumetric ratio of from 1:10 to 10:1 before being fractionated in a single unit to form the synthetic hydrocarbon feed of step c).
  • the wax fraction of step a) may have a true boiling point (TBP) in the range of about 70° C. to 700° C., typically in the range 80° C. to 650° C.
  • the FT condensate fraction of step b) may have a true boiling point (TBP) in the range ⁇ 70° C. to 350° C., typically ⁇ 10° C. to 340° C., usually ⁇ 70° C. to 350° C.
  • TBP true boiling point
  • the synthetic hydrocarbon fraction usable as feedstock for thermal cracking may be a C5 to 160° C. boiling range, defined based on the ASTM D86 Distillation standard, synthetic naphtha.
  • a semi-synthetic feedstock may be produced which is usable for the production of lower olefins via thermal cracking, said feedstock comprising an olefinic synthetic feedstock obtained from a FT synthesis product of H 2 and CO and a highly paraffinic fraction selected from a petroleum liquid fraction and a natural gas liquid fraction, blended to have at least a 15% mass olefins content and an aromatics content below 1%.
  • the highly paraffinic naphtha may be a product obtained from conventional petroleum refining scheme or from the fractionation of the liquid hydrocarbons contained in natural gas.
  • the blending ratio required is selected for each specific highly paraffinic naphtha in order to obtain a semi-synthetic naphtha with a similar olefins content as that of the above described fully synthetic naphtha, i.e. in the range of more than 15% or more than 20% by mass together with an aromatics content below 1% mass.
  • Table 1 gives a typical composition of the two FT liquid fractions obtainable from a FT reactor.
  • TABLE 1 Typical FT product after separation into two fractions (vol. % distilled) Distillation FT Condensate FT Wax Range ( ⁇ 270° C. fraction) (>270° C. fraction) C 5 -160° C. 44 3 160-270° C. 43 4 270-370° C. 13 25 370-500° C. — 40 >500° C. — 28
  • Catalysts for the FT wax hydroprocessing are typically of the bifunctional type; i.e. they contain sites active for cracking and for hydrogenation.
  • Catalytic metals active for hydrogenation include group VIII noble metals, such as platinum or palladium, or a sulphidcd Group VIII base metals, e.g. nickel, cobalt, which may or may not include a sulphided Group VI metal, e.g. molybdenum.
  • the support for the metals can be any refractory oxide, such as silica, alumina, titania, zirconia, vanadia and other Group III, W, VA and VI oxides, alone or in combination with other refractory oxides. Alternatively, the support can partly or totally consist of zeolite. However, for this invention the preferred support is amorphous silica-alumina.
  • Process conditions for hydrocracking can be varied over a wide range and are usually laboriously chosen after extensive experimentation to optimise the yield of naphtha.
  • Table 2 gives a list of one such set of conditions. TABLE 2 Process conditions for hydrocracking of the FT Wax BROAD PREFERRED CONDITION RANGE RANGE Temperature, ° C. 150-450 340-400 Pressure, bar-g 10-200 30-80 Hydrogen Flow Rate, m 3 n /m 3 feed 100-2000 800-1600 Conversion of >370° C. material, mass % 30-80 50-70
  • a basic process for the preparation of synthetic hydrocarbon feed is outlined in FIG. 1.
  • a synthesis gas (syngas) stream 11 enters the FT reactor 1 where the synthesis gas is converted to hydrocarbons by the FT reaction.
  • a waxy FT fraction is recovered in line 13 and sent to the hydroconversion unit 2 .
  • the hydroprocessed product is sent to fractionator unit 3 where at least three products are recovered: hydroprocessed naphtha 17 , hydroprocessed diesel 18 , and unconverted waxy species that might be recycled to unit 2 via line 19 .
  • the synthetic hydrocarbon feed of this invention may be produced either by blending streams 12 a and 17 (as shown in FIG. 1) when two fractionators are included in the process scheme or as a single stream 17 (as shown in FIG. 2) when only one fractionator is used.
  • the synthetic hydrocarbon feed is a naphtha product which comprises typically a C 5 -160° C. fraction and are useful as petrochemical naphthas.
  • the blending ratio for naphtha streams 12 a and 17 obtainable when including two fractionators can range from 1:2 to 2:1, typically the ratio is between 2:3 and 3:2.
  • the blending ratio for naphtha 12 and hydro processed wax 15 can range from 1:10 to 10:1.
  • a somewhat heavier cut, synthetic diesel is also obtainable by blending streams 12 b (olefinic distillate) and 18 (hydroconverted distillate) when two fractionators are included (FIG. 1) when two distillate fractions are recovered.
  • streams 12 b olefinic distillate
  • 18 hydroconverted distillate
  • an equivalent product can be recovered as stream 18 as shown in FIG. 2. These two products can be used on their own or blended as a single product. All of these distillate cuts are typically recovered as 165-370° C. fractions useful as diesel fuel.
  • the heavy unconverted material 19 from fractionator 3 is typically recycled to extinction to hydroconversion unit 2 .
  • the residue may be used for production of high viscosity index synthetic lube oil bases.
  • the synthetic hydrocarbon feed including an unhydrogenated FT fraction was prepared using the process as described above as was a fully hydroprocessed synthetic hydrocarbon feed for comparative testing.
  • the characteristics of these two feeds are set out in Table 3.
  • Naphtha 1 is a fully hydroprocessed FT naphtha with a 0.5% residual olefins content.
  • Naphtha 2 is an olefinic FT naphtha prepared using a process scheme such as that described in FIG. 2. Its olefins content was 21.9%.
  • the Cracking severity was measured by calculating the Propylene/Ethylene (P/E) mass ratio. Note that P/E ratio has an inverse relation to the cracking severity: high P/E ratios correspond to low severities (i.e. lower cracking temperatures) and lower methane co-produced.
  • the lower olefins of commercial interest are ethylene, propylene and butadiene.
  • the thermal cracking process also results in the production of unsaturated liquid hydrocarbons with five or more carbon atoms (C5). This product is of low commercial interest to thermal cracker operators.
  • a semi-synthetic naphtha whose olefin content is similar to that of the olefinic Naphtha 2 can be prepared by blending the FT straight run Naphtha 3 fractionated from the FT condensate with a highly paraffinic conventional petrochemical naphtha.
  • the composition of two of 10 these products is presented in Table 5.

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US10/358,129 2003-01-31 2003-01-31 Process for the preparation of and composition of a feedstock usable for the preparation of lower olefins Abandoned US20040149629A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US10/358,129 US20040149629A1 (en) 2003-01-31 2003-01-31 Process for the preparation of and composition of a feedstock usable for the preparation of lower olefins
CN200480005586.5A CN1756828B (zh) 2003-01-31 2004-01-30 可用作制备低碳烯烃的原料的组合物及其制备工艺
ES200550048A ES2279717B1 (es) 2003-01-31 2004-01-30 Proceso para la preparacion de una carga y composicion de dicha carga utilizable para la preparacion de olefinas inferiores.
JP2006503927A JP4543033B2 (ja) 2003-01-31 2004-01-30 低級オレフィンの調製のため使用可能な供給原料の調製方法および組成
GB0515611A GB2412921B (en) 2003-01-31 2004-01-30 Process for the preparation of and composition of a feedstock usable for the preparation of lower olefins
BR0407158-1A BRPI0407158A (pt) 2003-01-31 2004-01-30 Processo para a preparação de olefinas inferiores a partir de uma alimentação de hidrocarboneto sintético, alimentação de hidrocarboneto para um processo de craqueamento para a preparação de olefinas inferiores, processo para a preparação de uma alimentação de hidrocarboneto sintético, e, matéria-prima semi-sintética
CN200710089556.2A CN101033408A (zh) 2003-01-31 2004-01-30 由合成烃原料制备低碳烯烃的热裂化方法
AU2004207852A AU2004207852B2 (en) 2003-01-31 2004-01-30 Process for the preparation of and composition of a feedstock usable for the preparation of lower olefins
PCT/ZA2004/000012 WO2004067486A2 (en) 2003-01-31 2004-01-30 Process for the preparation of and composition of a feedstock usable for the preparation of lower olefins
ZA200505976A ZA200505976B (en) 2003-01-31 2005-07-26 Process for the preparation of and composition of a feedstock usable for the preparation of lower olefins
US11/707,366 US20070203386A1 (en) 2003-01-31 2007-02-15 Process for the preparation of and composition of a feedstock usable for the preparation of lower olefins

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BR (1) BRPI0407158A (enExample)
ES (1) ES2279717B1 (enExample)
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US7431821B2 (en) 2003-01-31 2008-10-07 Chevron U.S.A. Inc. High purity olefinic naphthas for the production of ethylene and propylene
GB2399090B (en) * 2003-01-31 2005-06-08 Chevron Usa Inc High purity olefinic naphthas for the production of ethylene and propylene
KR100904297B1 (ko) 2007-10-26 2009-06-25 한국화학연구원 연속적인 2단계 촉매 반응을 이용한 합성가스로부터 경질올레핀의 제조방법
US8802899B2 (en) * 2008-06-09 2014-08-12 Solvay Specialty Polymers Italy S.P.A. Method for manufacturing perfluorovinylethers

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JP4543033B2 (ja) 2010-09-15
WO2004067486A2 (en) 2004-08-12
ES2279717B1 (es) 2008-08-01
CN1756828A (zh) 2006-04-05
CN1756828B (zh) 2011-03-02
GB2412921B (en) 2007-07-11
GB0515611D0 (en) 2005-09-07
US20070203386A1 (en) 2007-08-30
BRPI0407158A (pt) 2006-02-07
JP2006517254A (ja) 2006-07-20
GB2412921A (en) 2005-10-12
WO2004067486A3 (en) 2004-12-09
ZA200505976B (en) 2007-10-31
AU2004207852A1 (en) 2004-08-12
ES2279717A1 (es) 2007-08-16

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