[go: up one dir, main page]

WO2017086985A1 - Procédé et produit de brai en une seule étape - Google Patents

Procédé et produit de brai en une seule étape Download PDF

Info

Publication number
WO2017086985A1
WO2017086985A1 PCT/US2015/061745 US2015061745W WO2017086985A1 WO 2017086985 A1 WO2017086985 A1 WO 2017086985A1 US 2015061745 W US2015061745 W US 2015061745W WO 2017086985 A1 WO2017086985 A1 WO 2017086985A1
Authority
WO
WIPO (PCT)
Prior art keywords
pitch
feed
reactor
product
gasoline
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.)
Ceased
Application number
PCT/US2015/061745
Other languages
English (en)
Inventor
Donald P. Malone
Donald M. Lee
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to EP15908972.1A priority Critical patent/EP3377594A4/fr
Priority to PCT/US2015/061745 priority patent/WO2017086985A1/fr
Priority to CN201580084333.XA priority patent/CN108291151A/zh
Publication of WO2017086985A1 publication Critical patent/WO2017086985A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/19—Working-up tar by thermal treatment not involving distillation
    • 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
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/18—Apparatus
    • C10G9/20—Tube furnaces
    • 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
    • C10G9/24—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by heating with electrical means
    • 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
    • C10G9/40—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by indirect contact with preheated fluid other than hot combustion gases
    • 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
    • C10G2400/02—Gasoline

Definitions

  • This invention relates to a continuous process for the manufacture of highly aromatic pitches from aromatic oils for use in producing molded carbonaceous articles such as anodes used in aluminum manufacture, impregnation pitch, and the manufacture of carbon artifacts, general purpose fibers, conversion into mesophase and high performance fibers.
  • pitch denotes a wide range of products. The term goes back to at least the description of Arthur's Ark given in the book of Genesis in the Old Testament. Some commentators opined that Arthur "cooked” pine sap in a clay pot, inducing thermal polymerization to form a higher softening point material. Others have suggested that Arthur's pitch was charcoal mixed with boiling pine tar. Still others have suggested that Arthur used natural oil seeps. No one knows what pitch process Arthur used and even today the term pitch is used to denote both naturally occurring heavy materials, such as seeps and those formed by thermal polymerization of lighter materials, such as pine sap cooked in a clay pot.
  • a residual material such as asphalt can be made from crude oil which is a complex mixture of hydrocarbons, some of which are so heavy or high in molecular weight as to be essentially non-distillable.
  • the non- distillable residue from such heavy crude is an asphaltic fraction, but is sometimes referred to as pitch.
  • a pitch product as used herein is the result of thermally induced polymerization of an aromatic rich liquid feed material usually obtained by distillation. The aromatic rich liquid is given sufficient thermal treatment to induce thermal polymerization, some thermal cracking, and thermal dealkylation.
  • One product is a mix of components lighter than the feed and the other, a thermally polymerized heavy product that is essentially non-distillable.
  • the two materials asphalt and pitch are easy to distinguish in practice.
  • a simple test illustrates the different natures of the two materials. Heat a liter or so of each and pour it on a desk. The asphalt forms a sticky mess which is difficult to remove.
  • a petroleum or coal tar pitch forms a glassy solid which after being hit with a hammer shatters into pieces which can be cleanly swept up in a dustpan leaving a relatively clean desk.
  • the primary pitch forming reactions are thermal, not catalytic, so it is possible to compare to some extent the "severity" of pitch forming reactions in one patent to conditions reported in another.
  • the primary mechanism for pitch formation is thermal polymerization.
  • Other reactions go on as well, including thermal cracking, thermal dealkylation of alkyl side chains of large molecules in the feed, and breakdown of complex large molecules, such as porphyrins.
  • the desired pitch product is primarily made by thermally induced polymerization.
  • Most of the other reactions, e.g., thermal cracking and dealkylation are also thermal reactions and so their contribution to pitch formation and byproduct formation can also be quantified using time and temperature. Because of the importance of understanding what is different about our new process from the old, a review of refining history and various thermal processes is needed.
  • coking which can thermally polymerize and thermally crack a heavy residual feed into a low value coke and more valuable lighter products.
  • the coke is usually a distress product, but the lighter products which contain large amounts of olefins and dienes can be converted into gasoline.
  • Coking conditions are so severe that long chain molecules are cracked into olefinic molecules which in turn are cracked to form reactive dienes.
  • the aromatic molecules are cracked and/or thermally polymerized all the way to a solid or coke product.
  • Coker naphtha is one of the main byproducts, but is unstable and difficult to process primarily because of the diene content. If attempts are made to process it in a typical fired heater in a refinery, the heater will coke up in a day or two. If coker naphtha is used in a car as gasoline, it forms gum and rapidly clogs filters, injectors and the like.
  • Thermal severity ranged from mild to severe. To quantify where a refinery process was on the thermal severity spectrum and compare one visbreaker to another when temperatures and flow rates were not the same was difficult. Thermal reactions increased exponentially and roughly doubled for every 10°C increase in temperature. Because temperatures of around 800°F were widely used for visbreaking, refiners introduced the concept of Equivalent Reaction Time at 800°F, or ERT seconds. Visbreaking is kinetically a first-order reaction. The severity of visbreaking is often expressed as ERT (equivalent residence time at 800°F in seconds) and is calculated by multiplying the cold oil residence time above 800° F by the ratio of relative reaction velocities as defined by Nelson (W. L. Nelson, Petroleum Refinery Engineering, 4th Ed., FIG. 19-18, page 675) taking into consideration the temperature profile across the visbreaker coil, using the average temperature for each one foot segment of the coil above 800°F.
  • ERT Equivalent Reaction Time at 800°F
  • polymerization of aromatic molecules to form pitch with a softening point of 200 - 400 °F or higher requires more severe thermal processing than visbreaking, but less severe operation than coking.
  • ERT is a way to compare severity and predict product yields from a given charge stock subjected to a given thermal treatment.
  • visbreaking or thermal cracking achieves moderate conversion of heavy feed to lighter products including an olefinic naphtha.
  • Coking achieves complete conversion of heavy feed to lighter products such as coker naphtha, but the olefin and especially the diene contents of the naphtha are so high that further treatment is needed.
  • Large complex refineries have the specialized equipment needed to process coker naphtha. Typically either a treatment at relatively low temperature over proprietary catalyst to saturate the dienes or mixing with conventional naphtha and hydrotreating at two to three times the pressure required for the hydrotreating other refinery naphtha fractions is used.
  • the severe hydrotreating of coker naphtha saturates the olefins significantly reducing the octane, so further treatment as in a platinum reformer is needed.
  • a given crude oil, or fraction thereof, subjected to a typical visbreaking severity of 800 ERT seconds will give essentially the same yield of gas and liquid products with essentially the same product composition. It matters not if the actual temperature used to process the feed was above 800°F for a time shorter than 800 seconds, or below 800°F for a longer period, the amount of thermal processing or thermal severity of the treatment will be the same. If two feedstocks have different chemical composition then the products from thermal processing will be different, even though the thermal severity used to treat the two feeds was identical. Thus ERT or some similar method of comparing the severity of one thermal process to another is an important and useful concept in understanding our and prior art processes.
  • ERT is a useful and helpful concept for analyzing what goes on in a pitch process and in comparing one pitch process to another.
  • pitches Physical properties of various pitches can be as different as their end uses. On a crude level, the softening point and coking value can vary greatly depending on how severe the pitch processing was and how much light material was left in or added to the residual pitch product. For some uses such as the manufacture of clay pigeons for target shooting, any pitches potentially can be used. For binder pitch used to form anodes for aluminum production, pitches from petroleum or from coal tar may be used, but coal tar pitch is preferred due to its high coking value. For impregnation of electrodes used in electric arc furnaces for steel manufacture, petroleum pitch e.g., made from FCC slurry oil is superior to all other
  • pitches For manufacture of carbon fibers, special high softening point pitches, usually having a softening point above 300°F or higher are needed. Petroleum pitches are generally preferred but coal tar pitch, with additional treatment steps may also be used. If there are concerns about BPA or other carcinogens, these can be significantly higher in coal tar pitch than petroleum pitch.
  • pitch manufacturing has been practiced for millennia, the process is not easy. It is easy to take any polymerizable material, pine resin, coal tar, slurry oil or the like and heat it to induce thermal polymerization and make pitch. The hard part of the process is avoiding going too far, since the end point of thermal polymerization is coke. Coke fouls the process equipment and contaminates the pitch product.
  • Some processes take advantage of the propensity of heavy residual feeds to form coke. Athabasca tar sands are too heavy to process in a conventional refinery. Many heavy crudes are both too viscous and contain too much metal and other impurities to permit refining in a conventional refinery. For such difficult feeds refiners have installed cokers that heat the difficult feed to a temperature sufficient to induce thermal reactions and let the heated feed sit in a coke drum for hours or days. Most of the feed, typically about 2/3 by weight, is converted to lighter products, such as coker naphtha or coker gas oil. These can be processed with some difficulty in a conventional refinery. About one third of the feed ends up as coke which is a low value product. When high quality feeds such as slurry oils from a catalytic cracking unit or ethylene cracker bottoms are available and high quality coke products are desired, thermal processing can be used to produce high value products, e.g. needle coke.
  • high quality feeds such as slurry oils from a cat
  • pitch manufacturers take to avoid making coke or mesophase-contaminated isotropic pitch, various pitch making processes will be reviewed. In general, producers limit coke formation by limiting conversion. Mesophase contamination is avoided by limiting conversion or by allowing some mesophase or precursors thereof to form, followed by solvent extraction of the desirable pitch product. Some isotropic pitch processes will be reviewed first. In all processes using thermal polymerization, it is hard to achieve this polymerization without coking up the heater tubes used to reach these extreme temperatures. Hot metal surfaces promote coke formation on the walls of the tubes in the heaters and cause rapid fouling. Shifting some heating from a fired heater to internal combustion or other reactions with hot feedstock can reduce fouling.
  • coal tar is mixed with aromatic petroleum fractions and heat-treated.
  • the carbon particles in the pitch are detrimental to use of the pitch as an impregnating agent or as a precursor for producing carbon fibers.
  • US 3,318,801 by Alexander discloses thermal treatment of ethylene cracker bottoms at pressures no higher than 250 psig and generally less than 100 psig. Some of the examples operated at thermal soaking temperatures of 357°C (675°F) to 396°C (745°F) with residence times of more than one hour. The highest softening point reported for the pitches produced was 95°C (203°F). One example used a thermal soaking temperature of 455°C (850°F) and residence time of approximately one minute. The softening point of the pitch produced was 81°C (178°F). The last example required distillation of the thermal soaker product to produce the pitch product. The pitch yield was 30% of the charge material.
  • US 3,140,248 by Bell discloses multi-step thermal treatment of slurry oil to make pitch.
  • the slurry oil and 2 to 8 volumes of a recycled gas oil boiling range material are thermally cracked at 850° - 1050 °F to produce a thermally cracked stream which is quenched.
  • This quenched stream mostly gas oil boiling range material by weight, is fractionated to recover and recycle a "thermal gas oil” as an overhead product and a first stage product, a residual product, and a "thermal asphalt” fraction with a softening point of 130° to 180°F.
  • This "thermal asphalt” was then given a second stage of processing. It was heat soaked at 900° to 1100°F and 30 to 700 psig for 4 to 20 minutes to make pitch product.
  • a disadvantage of all of the processes described above is that the yields per pass of pitch from the feedstocks are low. This increases the volume and cost of heating the reactor charge. More significantly, the recovery and reuse of large volumes of byproducts or unconverted feed is required to make the process viable. Fractionation is costly when relatively large amounts of light materials such as naphtha boiling range or light distillate materials must be removed from heavy distillate materials being recycled to the pitch heater. It is relatively easy to separate pitch which is a non-distillable material from gas oil and lighter materials, but much more work is required to separate, e.g., naphtha fractions from gas oil fractions. It is important, however, to remove the light material from recycled gas oil as the recycle of gasoline boiling range material would vaporize in the heater or soaking zone and effectively reduce the pressure and the pitch yield of the process.
  • Another fundamental challenge in producing highly aromatic pitch is operating at temperatures and residence times to maximize the yield of isotropic pitch without producing significant coke or mesophase. If the time and temperature are low, conversion rates are low. resulting in low yields. If the time and temperature are too high, coke can form, clogging equipment and/or producing pitch contaminated with coke particles. If conditions are severe, some mesophase can form and this is a contaminant when isotropic pitch is the desired product.
  • the prior art believed that to limit fouling of heater tubes or formation of undesired mesophase typically only a modest portion of the feed could be converted per pass.
  • the prior art generally converted an aromatic rich feed into pitch using a two step process. First, a fairly vigorous thermal treatment in a fired heater usually at a moderate pressure was followed by quenching and separation of some of the lighter products of thermal cracking from a thermal tar. Then an additional step, or steps, converted the thermal tar into pitch.
  • Tsuchitani US 4,925,547, taught a multi-step process to make isotropic pitch.
  • the first stage at about 300 psia in a small tubular reactor made a heavy oil, with some settling.
  • the oil was given an extraction treatment.
  • the extract phase was fractionated to remove solvent, then given additional thermal treatment to produce isotropic pitch, but yields were less than 20 wt % based on fresh feed.
  • the settlings or reject phase was given additional treatments to produce mesophase.
  • coking value is important. As would be expected, there is a relationship between softening point and coking value. Material with a low softening point has a low coking value since much of the "pitch" is oil.
  • the target for many petroleum pitches with a softening point of 230 - 240°F is a coking value of 50. For some uses a higher coking value of about 55 is needed.
  • coal tar pitch has a significantly higher coking value than a similar softening point petroleum pitch. The higher coking value of coal tar pitch is modest, usually an increase of 5 or so in coking value, but the slightly higher coking value of coal tar pitch is important enough that for many applications petroleum pitch is not used commercially.
  • the gasoline fraction by its small volume and unusual aliphatic character was also a "marker" that something different was going on in our process.
  • Our process required high temperatures and sufficient residence time to make pitch, but did not make unstable gasoline.
  • the present invention provides a process for producing isotropic pitch comprising charging a feed comprising distillate boiling range aromatic rich liquid and an optional distillate boiling range recycle material to an inlet of a tubular or pipe reactor and heating said feed within said reactor at a temperature sufficiently high to induce thermal polymerization of said feed and a pressure sufficient to maintain at least a majority by weight of said feed in liquid phase, and passing said feed through said reactor for a time sufficient to convert at least a portion of said feed to isotropic pitch and gasoline boiling range material, discharging from said reactor an effluent stream comprising pitch product and byproducts, and recovering isotropic pitch as a product of the process and wherein the time and temperature in said reactor create thermal conditions sufficient to convert at least 20 wt % of said feed and any recycle material which may be present and said pressure is sufficiently high to suppress mesophase formation.
  • the present invention provides a method of converting slurry oil into isotropic pitch, comprising charging a feed comprising slurry oil having a boiling range, at a temperature above 900°F to a tubular or pipe reactor and passing said feed through said reactor at a velocity of at least 1 m/s for a time sufficient to convert at least 20 wt % of said feed to a pitch product, unconverted or only partially converted material boiling within the same boiling range as the feed and lighter materials produced as a result of thermal cracking, thermal dealkylation, or thermally induced polymerization of said feed, and wherein a pressure in said reactor is maintained above 500 psig and sufficient to suppress mesophase formation to a predetermined amount in said isotropic pitch product; discharging into a flash drum operating at a pressure less than l/10 th said pressure in said reactor said pitch, said unconverted or partially converted feed and said lighter material; flashing from said flash drum a vapor phase comprising said unconverted or partially converted feed and said lighter material from
  • the present invention provides a process for thermally polymerizing an aromatic rich liquid obtained as a heavy product from the fluidized catalytic cracking process to produce isotropic pitch
  • a process for thermally polymerizing an aromatic rich liquid obtained as a heavy product from the fluidized catalytic cracking process to produce isotropic pitch comprising charging a slurry oil, clarified slurry oil, or filtered slurry oil feed to a tubular or pipe reactor having an inlet and an outlet and passing said feed through said reactor at thermal polymerization conditions including a temperature above 900°F, an average liquid velocity of at least 1 m/s, and outlet pressure of at least 500 psig to produce a reactor effluent comprising thermally polymerized isotropic pitch, unconverted feed or partially polymerized material and lighter liquid products having a lower boiling point than said feed and comprising gasoline boiling range materials and normally gaseous products; discharging said reactor effluent into a flash drum operated at a pressure from sub-atmospheric to 50 psig and flash
  • the present invention provides a high conversion, continuous process for making a flashable isotropic pitch product from a thermally
  • polymerizable multi-ring aromatic feedstock comprising fractionating a feedstock to remove, or selecting a feedstock having removed there from essentially all gasoline and lighter boiling range materials from a normally liquid hydrocarbon feed comprising multi-ring aromatic hydrocarbons to produce a pitch feedstock having a boiling range; charging said pitch feedstock to an inlet of a tubular or pipe reactor having an inlet and an outlet; thermally polymerizing, at thermal polymerization conditions including temperature, pressure and residence time, said pitch feedstock in said reactor at a temperature sufficiently high to thermally crack or thermally dealkylate a minor portion of said pitch feedstock to produce gasoline and lighter boiling range materials and wherein said temperature is also sufficiently high to thermally polymerize said pitch feedstock to isotropic pitch, to mesophase pitch and to coke; maintaining a pressure in said reactor sufficiently high to suppress mesophase formation to a predetermined level which is compatible with an isotropic pitch product and to suppress coke formation; discharging from said reactor a reactor effluent comprising gasoline and lighter boiling range materials, uncon
  • a process for converting a gas oil and heavier aromatic liquid feedstock comprising alkyl aromatic hydrocarbons, multi-ring aromatic hydrocarbons and having a boiling range into a gasoline fraction by thermal dealkylation, and isotropic pitch, by thermal polymerization comprising charging said feedstock to an inlet of a tubular or pipe reactor having an inlet and outlet; thermally polymerizing, at thermal polymerization conditions including temperature, pressure and residence time, said feedstock in said reactor at a temperature sufficiently high to thermally crack or thermally dealkylate at least a portion of said alkyl aromatics in said feedstock to produce gasoline and lighter boiling range materials and wherein said
  • temperature is also sufficiently high to thermally polymerize at least a portion of said feedstock to isotropic pitch, to mesophase pitch and to coke; maintaining the pressure in said reactor sufficiently high to suppress mesophase formation to a predetermined level which is compatible with an isotropic pitch product and to suppress coke formation; discharging from said reactor, a reactor effluent comprising gasoline and lighter boiling range materials, unconverted or partially converted feedstock boiling within the same range as said feedstock, and isotropic pitch; maintaining time and temperature in said reactor sufficiently high to convert a predetermined amount of said feedstock to isotropic pitch and maintaining said pressure within said reactor sufficiently high to force at least a portion of thermally cracked materials to be dissolved within liquid in said reactor and at least a portion of this dissolved, cracked material to react with material in said liquid phase of said reactor to form isotropic pitch, and discharging from said reactor a stream comprising gasoline and lighter material, unconverted or partially converted feedstock boiling within the boiling range of said feedstock, and isotropic pitch and wherein at least an
  • Figure 1 illustrates a schematic of an embodiment of the process.
  • Figure 2 illustrates a similar schematic of an embodiment of the process that has an additional liquid vapor separator to reduce vaporization, to reduce the degree of vaporization and to improve the control of product properties in downstream equipment.
  • Figure 3 illustrates an embodiment of heating equipment to precisely control the temperature of fluids flowing in a conduit.
  • Figure 4 illustrates an additional embodiment of the equipment described in fig 3.
  • Figure 5 illustrates two chemical reactions considered to be important in the production of pitch.
  • Figure 1 illustrates one embodiment of the process.
  • Figure 2 illustrates a second embodiment of the process.
  • Figure 3 illustrates a means to achieve precise, uniform temperature control of the process fluid.
  • Figure 4 illustrates a second embodiment of the device in Figure 3.
  • Figure 1 and Figure 2 are very nearly identical with the exception of an additional processing step in Figure 2.
  • the reference numerals in Figure 1 and Figure 2 are identical for corresponding equipment. The following description will describe either embodiment with noted exceptions where differences exist. Similarly Figures 3 and 4 are very similar. Common reference numerals in these figures refer to identical items. The description of Figure 4 will consider only the additional features in Figure 4 that are not in Figure 3.
  • Fresh feed 10 mixes with distillate recycle 82 and optionally water or steam injection 92 to comprise one fired heater inlet stream 12. Normally steam or water will not be added to the feed, as in some experiments discussed hereafter, steam addition caused significant mesophase production. It may still be beneficial to have some way of getting steam into the tubular reactor, to de-coke during some periods of operation should coke build up during normal operation or during an upset.
  • Some distillate recycle 80 may be heated separately in the fired heater 14.
  • the fired heater outlet temperature is 5° to 25°C below the reaction temperature.
  • the heater outlet streams 16 and 18 are heated to reaction temperature by precision heaters 20 and 22.
  • the outlet from the first precision heater 20 enters via line 26 a high shear precision temperature controlled reactor 28.
  • Some of the heated recycle material may be charged via line 24 and line 30 to combine with the outlet of the first reactor in line 34 to and charged via inlet 46 to the second high shear precision temperature controlled reactor 36. Some of the heated recycle material may pass via line 32 to combine with the outlet of the second reactor 38 to become the inlet 52 to a high, pressure high temperature flash vessel 40.
  • Hot, high-pressure vapor 42 from flash vessel 40 is cooled by a heat exchanger 44 to an intermediate temperature stream 86.
  • Second flash vessel 56 separates stream 86 into a vapor 58 and a liquid stream 62.
  • Recycle pump 64 discharge 66 may be recycled as stream 76 or withdrawn as product 84.
  • the pressure of stream 58 is reduced to a pressure appropriate for a fuel gas system and is further cooled by heat exchanger 60 to produce the inlet 88 to a third flash vessel 70.
  • Vapor 68 from the third flash is either further treated for use as fuel gas or burned in a flare.
  • a light liquid stream 72 is withdrawn as a product stream.
  • Hot, high-pressure liquid 48 from flash vessel 40 is throttled to a pressure appropriate for a fuel gas system and cooled to an intermediate temperature by heat exchanger 50 to become the inlet 90 to a fourth flash vessel 54.
  • the vapor 74 should be combined with the vapor 68 from the third flash vessel 70.
  • the liquid 78 from the fourth flash vessel 54 is withdrawn as a pitch product.
  • Figure 2 is identical to Figure 1 except that the outlet 34 of the first reactor 28 combined with the distillate recycle 30 to form 46 flows to a fifth flash vessel 110.
  • the vapor outlet 114 combines with vapor stream 42 to form stream 122 the inlet to heat exchanger 44, previously described.
  • Liquid 112 from the fifth flash vessel 110 will be heated if needed in a precision heater means 120.
  • the outlet 116 of heater 120 enters the second reactor 36 as stream 46 did in the description for Figure 1.
  • the purpose of this embodiment is to reduce the amount of vapor in the reactor system.
  • a third embodiment of this process uses multiple instances of vessels such as the fifth flash vessel 110 and multiple reactor means such as reactor 36 to further reduce the amount of vapor in the reactor system.
  • Figure 3 illustrates a preferred embodiment using a particular precision temperature heater and/or reactor means for very accurately and uniformly controlling the temperature of a fluid being heated and/or reacted.
  • a standard pipe or tube 11 of the appropriate metallurgy for these conditions Austenitic stainless steel), thickness, internal diameter and length is a flow conduit for the various streams heated or reacted in Figures 1 and 2.
  • Current sources 15, 17 and 19 add or withdraw current to or from the walls of conduit 11.
  • Electrical ground connections 13 and 21 ensure that no significant electrical current flows to other parts of the process. Electrical current passing through the length of the conduit wall produces heat proportional to the resistance of the conduit wall. No other electrical effect such as inductive coupling is intended.
  • One embodiment of this device uses direct current, DC as opposed to alternating current, AC. While AC will provide nearly identical resistance heating capabilities as DC, it may induce currents in unwanted equipment such as instruments and other electrically conductive materials. DC minimizes this effect.
  • the section between current source 15 and the ground connections could be the precision heater described earlier.
  • the section between current source 15 and current source 17 could be the first reactor.
  • the section between current source 17 and current source 19 could be the second reactor.
  • the section between current source 19 and ground connection 21 could be a third reactor.
  • a third embodiment of this device uses a coiled conduit 11.
  • the coils are sufficiently separated and electrically insulated such that there is no short-circuiting between the coils or to unintended electrical grounds.
  • a coiled arrangement allows for a compact reactor system for long conduit 11 lengths especially for conduit 11 outside diameters less than 25 mm.
  • a fourth embodiment of this device uses straight lengths of conduit 11 with 180° return bends.
  • the plane passing through the straight lengths of conduit can be vertical, horizontal or something intermediate. This arrangement also allows for a compact reactor system for long conduit 11 lengths especially for conduit 11 outside diameters greater than 50 mm.
  • a fifth embodiment of this device is illustrated in Figure 4. Provisions for additional recycle stream conduits 35 and 37 have been added to the device of Figure 3. Additional electrical current sources 23, 25, 27 and 29 have been added. Additional electrical grounds 31 and 33 have been added so that no significant electrical current flows outside the intended heating equipment. It should be noted that all current sources might either add or remove current such that any of the current sources could be an electrical ground. It should also be noted that the conduits 11, 35 and 39 could be of any length. The intended direction of fluid flow is from left to right for conduit 11 and from top to bottom for conduits 35 and 37.
  • conduits 11, 35 and 37 could be coiled, fitted with return bends or otherwise configured so that long sections of conduit could be accommodated in a compact space.
  • conduits 35 and 37 could be used as needed.
  • Precision heater means and reactor temperature control means other than that described above could be used in the process described in Figures 1 and 2.
  • skin effect induction could be used in place of the heaters and temperature controlled reactors described above.
  • HAP highly aromatic pitch
  • the methyl group most is the most predominate alkyl group found on these condensed rings.
  • the degree of ethyl substitution is typically much less than the degree of methyl substitution.
  • the degree of propyl substitution is typically much less than the degree of ethyl substitution and there are virtually no substituent groups heavier than propyl. Dealkylation and/or dehydrogenation of these rings under the conditions described herein are thermal reactions. These reactions are prohibitively slow below 400°C.
  • FIG. 5 illustrates these two types of reactions in the most basic way.
  • the top or first reaction is dealkylation.
  • the second or lower reaction is condensation. If condensation occurs over multiple instances, it may be considered to be polymerization or oligomerization.
  • the reactions shown in Figure 5 are given only for illustrative purposes. The reactions shown may not be the most likely to occur. The isomers shown may not even be present in some feeds.
  • Coke is almost entirely carbon. It does not melt or dissolve. Coke frequently forms on hot solid surfaces. Once formed on surfaces, coke can only be removed by extremely vigorous mechanical cleaning or combustion. As coke builds up on surfaces of equipment, it restricts fluid flow and impedes heat transfer. Coked equipment must be taken out of service to remove coke deposits. Coke formation is an important commercial consideration. Excessive coke formation can cause an otherwise profitable process to be uneconomical. Operating conditions and configurations must be carefully balanced to facilitate the rapid production of HAP, but minimize coke formation.
  • the new pitch (HAP) making process described herein can use any feedstock so long as it is sufficiently aromatic and has an appropriate boiling range. These materials are often characterized by methods developed by the American Petroleum Institute (API). A feedstock having an API gravity between -10° and +10° with an initial atmospheric boiling point greater than 288°C (550°F) and a final atmospheric boiling point of less than 704°C (1,300°F) is preferred. Although not preferred, the process can tolerate feedstock having an initial boiling point of 500°F, 450°F, or even 425°F to 400°F. These lighter feedstock materials can be used but generally do not have enough multi-ring aromatic compounds, and also contain too much readily vaporizable materials to make ideal feedstock.
  • API American Petroleum Institute
  • the petroleum stream most likely to meet the above requirements is slurry oil, sometimes referred to as decant oil, from refinery fluid catalytic cracking (FCC) operation. Distillation or other commercial separation processes may be able to create an acceptable feed from an otherwise unacceptable feed.
  • FCC refinery fluid catalytic cracking
  • Ethylene cracker bottoms are similar to slurry oils from FCC and can be used as feedstock. ECBs are derived from petroleum and are highly aromatic. Some fractionation or other feed preparation may be beneficial.
  • Coal tar can be used. Coal tar frequently contains impurities or chemical species which interfere with downstream uses. Our process tolerates small amounts of solids well, but some pretreatment to remove solids or quinoline insolubles may be needed. Coal tar light oil, middle, or middle heavy creosote oil and the like derived from destructive distillation of coal may also be used. All such liquids contain aromatic rings and may be used, though not necessarily with equivalent results.
  • the process works best when the feedstock contains little or no water, little or no gasoline boiling range material, and with essentially all of the feedstock preferably in the distillate boiling range.
  • gasoline could be a light naphtha fraction, boiling below 350°F or even a heavy naphtha fraction with an end boiling point of 400 or even 425°F.
  • the feed is a distillate boiling range material and preferably most of the feed is aromatic.
  • our process permits one to take a conventional feedstock, e.g. a slurry oil, and convert it in a single step to a pitch product, it is also possible to operate with a feedstock which has been subjected to some other conventional pitch conversion process.
  • the prior art pitch processes usually operated with very modest conversions per pass. It is possible to charge a feedstock containing some isotropic pitch, say between 0 and 5 wt % isotropic pitch, or even up to 10 wt % isotropic pitch, and upgrade this low softening point material using the process of the present invention. This approach may be especially beneficial when a prior art process can not make an isotropic pitch with the desired coking value.
  • Such off spec pitch product can be upgraded or converted to a higher softening point isotropic pitch by being charged to a tubular reactor in accordance with the teachings herein. It is important that any charge stock not have significant mesophase content, as any mesophase material in the feed will remain as mesophase material or be converted into coke.
  • temperature profile is possible where one wants to impose an increasing or decreasing temperature profile. Some operators will prefer to use temperature profile to change process conditions to account for variations in available feedstocks or product required. For simplicity, many will prefer to charge a relatively cool, or at least much cooler than the desired thermal reaction temperature, feed to the inlet and allow a portion of the tubular reactor to operate as a preheating section.
  • Salt baths are another good way to obtain the even heating desired. Salt baths have been used for almost a century for heating petroleum fluids, such as the Houdry case thermal cracking reactors developed in the 1920s.
  • the feed may be preheated in a direct fired portion of the heater with the tubular reactor within and heated by the convection section of the heater. Feed in the preheater portion likely will not enjoy even heating, but the temperatures are well below coking temperatures so minor hot spots on the tube can be calculated. As no combustion occurs downstream of the direct fired portion of the heater, the tubular reactor may be heated by the hot combustion gas discharged from the heater, and this hot gas does not generally create hot spots.
  • any type of heater may be used so long as it avoids hot spots, we prefer electric heating for superior control of temperature.
  • the temperature in the thermal reactors varies by less than 5°C, preferably less than 2 or 3°C, from inlet to outlet and may be controlled to within 5°C, preferably within 1° or 2°C, of the desired reaction
  • tubular reactor it is acceptable to have some portion of the tubular reactor operate at relatively low temperature as a preheater. It is also possible to have staged temperatures, i.e. starting with a relatively low temperature and progressively increasing temperatures. We prefer for simplicity of operation and control to run the tubular reactor at one temperature and to keep the temperature from inlet to outlet essentially uniform and to maintain velocity and mixing intensity in the tube sufficient to keep the maximum temperature difference, measured from the tube inner wall to the tube centerline, below 2°C, preferably below 1°C, and ideally 0.5°C or less.
  • the temperature can vary greatly from 850° to 1050°F, preferably 910° to 990°F, and more preferably 930° to 970°F.
  • Residence time in the tubular reactor can vary greatly. As stated previously, time and temperature are both necessary for determining the severity of a given reaction. Perhaps the easiest way to specify time, or rather time at a given temperature, is in functional terms, namely the degree of conversion of aromatic rich liquid into a pitch product. For purposes of this exercise, pitch product could be considered as that material with a softening point above
  • the process can perhaps work with pressures as low as 400 psig, but that may require careful feed pretreatment to produce a sufficiently heavy charge stock. We believe that 500 psig is a practical minimum, with higher pressure preferred. We ran our experiments at 900 psig outlet for the tubular reactor and achieved good results, as long as we did not add steam to the feed.
  • the prior art pitch plants made pitch in multiple stages, with the first stage of thermal treatment being little more than dealkylation or limited thermal polymerization.
  • the first stage of US 4,925,547 produced a "thermally cracked heavy oil" after heat treating in a tubular reactor at 470 - 520°C, 20 Kg/cm2, the reactor having an id of 6 mm, 40 m length. This heavy oil had some pitch components but was not close to being a pitch product.
  • the US 3,140,248 patent first stage thermal treatment yielded "thermal asphalt” with some pitch components, as evidenced by a 158 - 160°F softening point.
  • This thermal asphalt required further treatment in a soaking zone to make product pitch.
  • the conversion per pass in the first stage was low, the examples showed a 3:1 recycle ratio.
  • the process was run at 400 psig outlet pressure. It produced significant amounts of gasoline, and lighter, material.
  • the yield of gasoline was 16.0 to 15.3 wt % in several examples as compared to yields of "thermal asphalt” of 62.8 to 61.0 wt %, all yields based on syntower bottoms charged. While the process made some pitch, or pitch product precursors, the gasoline: pitch precursor weight ratio was about 1:4.
  • the new pitch (HAP) process described herein incorporates a number of features that maximize pitch yield while minimizing coke formation. Dealkylation and condensation reactions generally occur at a similar to significantly higher temperature and a higher pressure than previously described processes. The reactions occur in conduit at a severity and velocities significantly higher than in previously described processes.
  • Reynolds number is a dimensionless number and a good way of characterizing the kind of flow which is needed to make the process work, although hard to apply with accuracy to our process due to two phase flow.
  • Laminar flow typically occurs in pipes when the NRe is below about 2300 while turbulent flow occurs above 4000.
  • turbulent flow almost by definition, implies that the velocity in a pipe is the same across the pipe, the common use of this term ignores the significant boundary layer which forms near the pipe wall.
  • turbulent flow is just occurring, there will be a significant boundary layer near the tube wall where fluid moves slower. It is essential in our process to have a sufficiently high NRe so that there is very little in the way of a boundary layer. Some boundary layer can be tolerated as a slightly longer residence time does not equal coke formation.
  • Flow in the tube is believed to be fully developed turbulent flow.
  • a NRe above 10,000 is preferred, with an NRe above 25,000 giving better results.
  • Shear rate is another important factor and may be more useful than NRe.
  • turbulent flow shear rate is greatest near the wall and decreases rapidly toward the center of the pipe or tube. It is zero in the center.
  • the flow regime in the conduit tends toward annular or mist annular where all of the vapor and some of the liquid flows at high velocity in the core of the conduit while an annular ring of liquid flows along the conduit wall. In this circumstance nearly all of the shear rate occurs in the liquid film.
  • Quantitative characterization of the shear rate is not generally possible, but the shear rate is proportional to the pressure drop due to flow per length of conduit. Typical pressure drop per unit length for our experiments were in the range of 0.05 psi/ft to 1 psi/ft.
  • Coal tar contains enough solids and undesirable species that solvent extraction has been used to remove them, e.g., solids and xylene insoluble as in the US 4,925,547 patent.
  • This type of pretreatment of coal tar is beneficial, but not essential for the practice of our invention provided the offending material left in the coal tar is acceptable in the product or can be removed by filtration.
  • Slurry oil often contains a small amount of catalyst from the FCC process.
  • FCC catalyst is predominately an alumino silicate with trace amounts of other metals. The typical range for ash in slurry oil is 0.01% to 0.05% wt. Feed slurry oil for some HAP applications where even low particulate levels are unacceptable can be filtered to remove virtually all FCC catalyst.
  • HAP high viscous than slurry oil.
  • HAP filtration must be performed at a temperature of at least 204°C (400°F) and often higher in order to get a reasonable filtration rate. A filtration temperature this high precludes the use of many filter media that would otherwise be economically attractive for this application.
  • the tube used to form the thermal reactor of the process should be selected to have sufficient hardness, and inertness, to withstand the severe conditions.
  • the electric heating method discussed in conjunction of the review of the Figures was used, but the invention is not limited to such a heating method. It will also be possible to use a tube which is immersed in a salt bath or molten metal bath, the convection section of a fired heater, or perhaps even in the radiant section of a fired heater. There may be problems with these other approaches such as shorter run lengths due to localized high temperatures or some reaction of the tube with salt or molten metal, but the thermal reactions experienced by the feed will be the same. Any heating method can be used which in practice, and this includes the volume and velocity of material flowing through the tubes, allows the feed to be heated to the desired temperature without exposing the feed to hot spots.
  • a metal tube was used in our experiments, but it is also possible to operate with a ceramic tube or metal tube which has a ceramic or other impervious coating on the inside wall of the tube.
  • This ceramic tube can be heated in an encasing metal layer or heated by immersion in a salt bath, molten metal bath or a conventional heater.
  • the purpose of the tube is to contain the product not to catalyze any reactions.
  • the preferred reactor design using metal tubes and electric heating is a new apparatus, a compact, robust simple design which affords, for an industrial process, almost the temperature control of a salt bath or molten metal bath, but with none of the mechanical difficulties or concerns about corrosion which are a concern when tubes are immersed at high temperature into either salt or molten metal.
  • the pitch products of the process are also believed to be unique.
  • all prior pitch processes from Father Arthur's to the present there is some variation in thermal severity.
  • constant and rapid stirring of the pitch pot would reduce, but not eliminate, variations in severity of thermal processing of the feed.
  • pitch processes using air combustion, fired heaters, or recirculation there was some variation in severity of pitch processing.
  • pitch processes using air combustion, fired heaters, or recirculation there was some variation in severity of pitch processing.
  • two stage pitch processes such as '547 and the Bell patent, the first stage of processing makes an intermediate product, then a second stage of processing makes pitch.
  • '547 there is very uniform processing in the first stage to make the intermediate product, but the product separation step and to a lesser extent the second stage or soaking step spreads out the residence time of the feed.
  • the process of the present invention using fully developed turbulent flow subjects each pitch precursor molecule to an almost identical severity of thermal processing.
  • the product will be very uniform, and the lighter molecules which are the byproduct of the thermal cracking and dealkylation reactions occurring during processing will have less olefin and diene content than a similar pitch product made using any prior process.
  • the reduced olefin and diene content is due to ensuring that no feed molecules experience unintended severe cracking due to long residence time.
  • Most of the reduction in unsaturated content is probably due to the high pressure and vigorous mixing allowing reactive unsaturated species produced during the course of thermal treatment to react with partially converted pitch molecules.
  • the process of the present invention affords better control of thermal polymerization. This can be important when tight control of product and even of byproduct properties is necessary.
  • pitch products that will have desired specifications with less fractionation or other treatment.
  • the pitch products of our process will inherently be more uniform as they were all subjected to essentially the same thermal treatment, unlike prior processes which have more variation in thermal processing and produce a more varied product.
  • the careful control of product properties is somewhat analogous to the different spectrum of an incandescent source as opposed to a laser. The process permits finer tuning of process conditions and product properties.
  • This fine tuning and narrow residence time of aromatic liquid in the thermal reactor may also contribute to a higher coking value pitch.
  • the process of the present invention can produce pitch with a softening point of 95°C and coking value of 50 wt %, and pitch with softening point of 111°C and coking value of 55 wt %. These coking values are significantly higher than heretofore achievable in a petroleum pitch.
  • Such tolls are costly because the gasoline and light distillate material are not pitch, nor can they be recycled to form more pitch. They do not contain enough aromatics to be a suitable pitch forming feedstock. They vaporize in the thermal reactor if recycled, and this is bad as the desired pitch forming polymerizations occur in liquid phase.
  • the gasoline distillate material is close enough in boiling range to the gas oil material so that simple flashing and condensation cannot be used to separate gasoline from distillate.
  • the gasoline can easily be separated in a multi-stage fractionator, but fractionation is a significant capital and operating expense.
  • the amount of gasoline or light distillate is so low that it is possible to use a simple flash drum on the thermal reactor effluent to vaporize all the distil la ble material, followed by sequential coolers to condense from these vapors a gas oil phase which is recycled and then condense a gasoline and light distillate phase which is removed.
  • a simple flash drum on the thermal reactor effluent to vaporize all the distil la ble material, followed by sequential coolers to condense from these vapors a gas oil phase which is recycled and then condense a gasoline and light distillate phase which is removed.
  • This gasoline fraction of course contains significant amounts of heavier materials, as simple cooling will not fractionate our gasoline material, but the amount of gasoline is so small that the loss of some potential recycle material can be tolerated.
  • Pressure is also a critical variable, both to reduce mesophase formation to levels which can be tolerated in the product and to reduce gasoline yields.
  • Mesophase formation is probably reduced by some mechanism involving keeping much or almost all of the multi-ringed aromatic structures in liquid phase.
  • the exact mechanism for the reduction of gasoline yields is not known. Intuitively, one would expect that as processing severity increased to achieve the required conversion levels, the gasoline yields would increase. In all other thermal processes, from visbreaking to coking, gasoline yields and the olefin and diene content thereof increase with increasing severity.
  • the higher pressures used probably promote olefin dimerization or polymerization, or higher pressures may favor the formation of higher molecular weight products and thus increase the yields of pitch and reduce yields of gasoline.
  • the mesophase content of the product must be kept at a low level to produce a good product.
  • Mesophase is also just a step away from coke formation and should be avoided for that reason.
  • Thermal severity or conversion should be increased until the desired conversion is achieved. It is possible to monitor the relative amounts of gasoline, recycle oil, and pitch product produced. At first there will be little or no product, but as severity increases greater amounts of pitch are produced. Gasoline yields will increase with increasing severity, but in our experience, the ratio of gasoline to pitch product will decrease at the relatively high conversion levels used. While mesophase production is especially sensitive to pressure, the low levels of mesophase in the product and the need to cool and polish a sample for optical inspection may make this approach unsuitable for close control of the process. The ratio of gasoline to pitch is not a product constraint but is a sensitive indicator of how the plant is operating. Severity can be increased until the ratio of gasoline to pitch, or gasoline to recycle oil, or light gas to pitch, or some other similar ratio, can be used to judge the severity of the process.
  • the process can be improved by in some cases by adopting some recycling or conversion paths.
  • the flash vapor produced is cooled in a cooling means sufficiently to condense at least a majority of unconverted or partially converted pitch feedstock, which is recycled to a tubular or pipe reactor for thermal polymerization to form additional amounts of isotropic pitch, and leave at least a majority of gasoline and lighter material as a vapor phase which is withdrawn as a product of the process.
  • thermal polymerization conditions are selected to produce an order of magnitude more isotropic pitch product than gasoline boiling range material, by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé et un appareil de fabrication de brai isotrope. L'invention concerne un réacteur tubulaire long fonctionnant à haute vitesse et haute pression pour convertir une charge liquide riche en aromatiques en brai en quelques minutes. Le réacteur peut être chauffé par un chauffage à résistance électrique ou à induction, l'immersion dans un bain de sel ou un bain de métal fondu, ou un four classique. L'effluent de réacteur est vaporisé, et du brai isotrope peut être récupéré à partir du séparateur instantané avec ajustement du point de ramollissement par actionnement du séparateur instantané à basse pression ou avec adjonction de vapeur d'extraction au séparateur instantané. Un matériau non transformé ou partiellement transformé éliminé sous forme de vapeur du séparateur instantané peut être refroidi et condensé pour récupérer ce matériau aux fins de recyclage. Le procédé de polymérisation thermique rend une si petite quantité d'essence qu'une condensation séquentielle simple de vapeur du séparateur instantané peut être utilisée pour obtenir une fraction à intervalle d'ébullition de gazole de recyclage puis une fraction à intervalle d'ébullition d'essence avec perte tolérable de gazole à la fraction essence, tolérable car la production d'essence est une si petite fraction du spectre de produit. Le brai de pétrole isotrope peut être fabriqué en une seule étape avec un excellent rendement de cokéfaction de 50 à 55 % en poids. La sévérité thermique telle que mesurée par le temps et la température dans le réacteur tubulaire est suffisante pour transformer au moins 20 % en poids de la charge et tout matériau de recyclage qui peut être présent en brai isotrope. La pression est maintenue suffisamment élevée, de préférence supérieure à 500 psig, afin de supprimer la formation de mésophases en dessous d'une quantité prédéterminée, par exemple, pour produire du brai isotrope avec moins de 0,5 % en poids de mésophases.
PCT/US2015/061745 2015-11-20 2015-11-20 Procédé et produit de brai en une seule étape Ceased WO2017086985A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP15908972.1A EP3377594A4 (fr) 2015-11-20 2015-11-20 Procédé et produit de brai en une seule étape
PCT/US2015/061745 WO2017086985A1 (fr) 2015-11-20 2015-11-20 Procédé et produit de brai en une seule étape
CN201580084333.XA CN108291151A (zh) 2015-11-20 2015-11-20 单级沥青工艺和产品

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2015/061745 WO2017086985A1 (fr) 2015-11-20 2015-11-20 Procédé et produit de brai en une seule étape

Publications (1)

Publication Number Publication Date
WO2017086985A1 true WO2017086985A1 (fr) 2017-05-26

Family

ID=58719124

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2015/061745 Ceased WO2017086985A1 (fr) 2015-11-20 2015-11-20 Procédé et produit de brai en une seule étape

Country Status (3)

Country Link
EP (1) EP3377594A4 (fr)
CN (1) CN108291151A (fr)
WO (1) WO2017086985A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108424780A (zh) * 2018-03-06 2018-08-21 国家能源投资集团有限责任公司 改性沥青及其连续生产方法与系统
WO2021015824A1 (fr) 2019-07-23 2021-01-28 Koppers Delaware, Inc. Procédé et système de traitement thermique pour des rendements accrus de brai
WO2023169486A1 (fr) * 2022-03-09 2023-09-14 中国石油大学 (华东) Système de réaction et procédé de préparation d'un brai mésophase de haute qualité et de co-production d'un brai isotrope filable
RU2837197C2 (ru) * 2019-07-23 2025-03-26 Копперз Делавэр, Инк. Процесс и система термической обработки с увеличенным выходом пека

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111518583B (zh) * 2020-04-20 2021-03-05 华中科技大学 一种固废热解液相产物熔盐梯级处理除杂提质装置
KR102866839B1 (ko) * 2020-07-13 2025-09-30 토마스 씨 홀컴 피치 공정 및 생성물
CN113882215A (zh) * 2021-10-20 2022-01-04 中电建冀交高速公路投资发展有限公司 一种沥青路面旧料沥青提取方法
CN117983167B (zh) * 2024-04-03 2024-07-19 克拉玛依市先进能源技术创新有限公司 一种中间相沥青、通用级沥青制备系统及方法

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3140248A (en) 1962-03-06 1964-07-07 Socony Mobil Oil Co Inc Process for preparing binder pitches
US3318801A (en) 1963-10-01 1967-05-09 Monsanto Co Production of petroleum base pitch and aromatic oils
US3673077A (en) 1968-10-03 1972-06-27 Shell Oil Co Process for producing electrode binder pitch and carbon black feedstock
US3725240A (en) 1971-05-13 1973-04-03 Mobil Oil Corp Process for producing electrode binder asphalt
US3970542A (en) 1971-09-10 1976-07-20 Cindu N.V. Method of preparing electrode pitches
US4096056A (en) 1976-10-21 1978-06-20 Witco Chemical Corporation Method of producing an impregnating petroleum pitch
US4663022A (en) * 1985-01-16 1987-05-05 Fuji Standard Research, Inc. Process for the production of carbonaceous pitch
US4705618A (en) 1984-10-29 1987-11-10 Maruzen Petrochemical Co., Ltd. Process for the preparation of an intermediate pitch for manufacturing carbon products
US4925547A (en) 1988-08-25 1990-05-15 Maruzen Petrochemical Co., Ltd. Process for producing pitch for the manufacture of high-performance carbon fibers together with pitch for the manufacture of general-purpose carbon fibers
JPH08120282A (ja) * 1994-10-25 1996-05-14 Showa Shell Sekiyu Kk 炭素繊維用等方性ピッチの製造法
US6352637B1 (en) 1998-12-31 2002-03-05 Marathon Ashland Petroleum, Llc High coking value pitch
US7318891B1 (en) * 2003-11-03 2008-01-15 Dtx Technologies Llc Noah's pitch process
WO2009074837A1 (fr) 2007-12-10 2009-06-18 Dtx Technologies Llc Production et fractionnement de brai et brai à point de ramollissement élevé
JP2014227545A (ja) * 2013-05-27 2014-12-08 ジーエス カルテックス コーポレイション 炭素繊維用ピッチの製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62277491A (ja) * 1986-05-26 1987-12-02 Maruzen Petrochem Co Ltd メソフエ−ズピツチの製法
DE3702720A1 (de) * 1987-01-30 1988-08-11 Bergwerksverband Gmbh Pechmaterial aus kohleteerpech, verfahren zu dessen herstellung sowie verwendung des pechmaterials
CA1302934C (fr) * 1987-06-18 1992-06-09 Masatoshi Tsuchitani Mode de preparation de brais mesophases
CN1167807A (zh) * 1996-05-31 1997-12-17 丸善石油化学株式会社 携带超细分散金属的含碳材料的制备方法
CN101292013B (zh) * 2005-10-20 2012-10-24 埃克森美孚化学专利公司 烃残油处理和减粘裂化蒸汽裂化器的原料
CN101525543B (zh) * 2009-04-07 2013-02-06 汝南县东旭碳材塑料有限公司 一种中间相沥青的制备方法
CN101885976B (zh) * 2010-07-02 2013-07-24 神华集团有限责任公司 从煤直接液化残渣中提取重质液化油和中间相沥青类物质的方法以及其应用
CN102704373A (zh) * 2011-07-04 2012-10-03 苏强 一种旧沥青混合料热再生加热方法及装置

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3140248A (en) 1962-03-06 1964-07-07 Socony Mobil Oil Co Inc Process for preparing binder pitches
US3318801A (en) 1963-10-01 1967-05-09 Monsanto Co Production of petroleum base pitch and aromatic oils
US3673077A (en) 1968-10-03 1972-06-27 Shell Oil Co Process for producing electrode binder pitch and carbon black feedstock
US3725240A (en) 1971-05-13 1973-04-03 Mobil Oil Corp Process for producing electrode binder asphalt
US3970542A (en) 1971-09-10 1976-07-20 Cindu N.V. Method of preparing electrode pitches
US4096056A (en) 1976-10-21 1978-06-20 Witco Chemical Corporation Method of producing an impregnating petroleum pitch
US4705618A (en) 1984-10-29 1987-11-10 Maruzen Petrochemical Co., Ltd. Process for the preparation of an intermediate pitch for manufacturing carbon products
US4663022A (en) * 1985-01-16 1987-05-05 Fuji Standard Research, Inc. Process for the production of carbonaceous pitch
US4925547A (en) 1988-08-25 1990-05-15 Maruzen Petrochemical Co., Ltd. Process for producing pitch for the manufacture of high-performance carbon fibers together with pitch for the manufacture of general-purpose carbon fibers
JPH08120282A (ja) * 1994-10-25 1996-05-14 Showa Shell Sekiyu Kk 炭素繊維用等方性ピッチの製造法
US6352637B1 (en) 1998-12-31 2002-03-05 Marathon Ashland Petroleum, Llc High coking value pitch
US7318891B1 (en) * 2003-11-03 2008-01-15 Dtx Technologies Llc Noah's pitch process
WO2009074837A1 (fr) 2007-12-10 2009-06-18 Dtx Technologies Llc Production et fractionnement de brai et brai à point de ramollissement élevé
JP2014227545A (ja) * 2013-05-27 2014-12-08 ジーエス カルテックス コーポレイション 炭素繊維用ピッチの製造方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
AVIDAN ET AL.: "Fluid Catalytic Cracking Report", OIL & GAS JOURNAL, 8 January 1990 (1990-01-08)
no. 68334-31-6, pages 675
See also references of EP3377594A4

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108424780A (zh) * 2018-03-06 2018-08-21 国家能源投资集团有限责任公司 改性沥青及其连续生产方法与系统
WO2021015824A1 (fr) 2019-07-23 2021-01-28 Koppers Delaware, Inc. Procédé et système de traitement thermique pour des rendements accrus de brai
US11248172B2 (en) 2019-07-23 2022-02-15 Koppers Delaware, Inc. Heat treatment process and system for increased pitch yields
CN114174470A (zh) * 2019-07-23 2022-03-11 考伯斯特拉华有限公司 提高沥青产量的热处理方法和系统
JP2022541649A (ja) * 2019-07-23 2022-09-26 コッパーズ デラウェア インコーポレイテッド ピッチ収率を増加するための熱処理プロセス及びシステム
US11624029B2 (en) 2019-07-23 2023-04-11 Koppers Delaware, Inc. Heat treatment process for increased pitch yields
JP7649603B2 (ja) 2019-07-23 2025-03-21 コッパーズ デラウェア インコーポレイテッド ピッチ収率を増加するための熱処理プロセス及びシステム
RU2837197C2 (ru) * 2019-07-23 2025-03-26 Копперз Делавэр, Инк. Процесс и система термической обработки с увеличенным выходом пека
WO2023169486A1 (fr) * 2022-03-09 2023-09-14 中国石油大学 (华东) Système de réaction et procédé de préparation d'un brai mésophase de haute qualité et de co-production d'un brai isotrope filable

Also Published As

Publication number Publication date
EP3377594A1 (fr) 2018-09-26
CN108291151A (zh) 2018-07-17
EP3377594A4 (fr) 2019-06-12

Similar Documents

Publication Publication Date Title
US9222027B1 (en) Single stage pitch process and product
WO2017086985A1 (fr) Procédé et produit de brai en une seule étape
RU2727803C1 (ru) Объединенные установки пиролиза и гидрокрекинга для превращения сырой нефти в химические продукты
KR101436174B1 (ko) 2개의 기액 분리기를 이용하여 중질 탄화수소 공급원료로부터 저급 올레핀을 생산하는 개량된 방법
TWI855045B (zh) 利用氫加成及脫碳之混合用以轉化原油及冷凝物為化學品之方法
TWI415931B (zh) 裂解含有合成原油的原料之方法
TWI500754B (zh) 蒸汽裂解烴類進料的方法與裝置
EP2421935B1 (fr) Procédé efficace pour obtenir une qualité améliorée de gas-oil de cokéfaction
EP0191207A1 (fr) Procédé pour améliorer le rendement en produits d'une cokéfaction retardée
WO2018104443A1 (fr) Procédé de prétraitement et de conversion d'hydrocarbures
KR100813896B1 (ko) 잔유를 함유한 탄화수소 공급원료의 증기 분해동안형성되는 코크스를 제거하기 위한 방법 및 장치
CN1957068A (zh) 含盐和/或微粒物质的烃原料的蒸汽裂化
US8277639B2 (en) Steam cracking of high TAN crudes
WO2008070300A1 (fr) Régulation du brai par trempe d'un effluent craqué provenant d'un craqueur de gaz alimenté par liquide
US5350503A (en) Method of producing consistent high quality coke
US8118996B2 (en) Apparatus and process for cracking hydrocarbonaceous feed utilizing a pre-quenching oil containing crackable components
CN114901786A (zh) 从原油中生产轻质烯烃的方法
CN104736677A (zh) 焦炭鼓添加剂注入
US20040173504A1 (en) Coker operation without recycle
NL8102085A (nl) Werkwijze voor het bereiden van pek uit aardoliefrakties en de aldus verkregen pek.
EP2707459B1 (fr) Procédé et appareillage pour produire du coke à matières combustibles volatiles élevée
KR102455669B1 (ko) 파울링 경향이 높은 중질 피치 및 다른 공급 원료의 현장 코킹
RU2805662C1 (ru) Способ и установка для получения нефтяного игольчатого кокса замедленным коксованием
Wisecarver Delayed coking
RU2775970C2 (ru) Коксование на месте тяжелого пека и другого сырья с высокой тенденцией к загрязнению

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15908972

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2015908972

Country of ref document: EP