[go: up one dir, main page]

WO2017009785A1 - Compositions, leur procédé et leurs applications - Google Patents

Compositions, leur procédé et leurs applications Download PDF

Info

Publication number
WO2017009785A1
WO2017009785A1 PCT/IB2016/054175 IB2016054175W WO2017009785A1 WO 2017009785 A1 WO2017009785 A1 WO 2017009785A1 IB 2016054175 W IB2016054175 W IB 2016054175W WO 2017009785 A1 WO2017009785 A1 WO 2017009785A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
coke
hydrocarbon cracking
cracking
during
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/IB2016/054175
Other languages
English (en)
Inventor
Padmavathi GARIMELLA
Sumeet Kumar SHARMA
Nagesh Sharma
Raksh Vir Jasra
Laxmilal Jain
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.)
Reliance Industries Ltd
Original Assignee
Reliance Industries Ltd
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 Reliance Industries Ltd filed Critical Reliance Industries Ltd
Priority to US15/744,405 priority Critical patent/US20180208856A1/en
Priority to EP16745176.4A priority patent/EP3322773B1/fr
Priority to KR1020187003920A priority patent/KR20180042849A/ko
Publication of WO2017009785A1 publication Critical patent/WO2017009785A1/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
    • 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
    • C10G9/16—Preventing or removing incrustation
    • 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
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
    • 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
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4075—Limiting deterioration of equipment

Definitions

  • the present disclosure relates to the field of organic chemistry, particularly steam cracking of hydrocarbons.
  • the disclosure relates to a composition comprising inorganic salts including but not limiting to Group 1A and Group 2A metallic salts, respectively.
  • the composition of the present disclosure is employed for reducing formation and/or deposition of coke in the systems employed for high temperature processing or cracking of hydrocarbons.
  • the present disclosure also relates to addition of a composition comprising inorganic salts including but not limiting to Group 1A and Group 2 A metallic salts into the system employed for cracking of hydrocarbons.
  • the present disclosure thus provides a composition comprising metallic salts such as potassium carbonate and calcium acetate, and a method of employing the same to reduce coke formation and/or deposition during cracking of hydrocarbons.
  • the disclosure also exemplifies a system wherein said method and composition is employed for said reduction of coke.
  • Coke formation is linked to or is a result of complex mechanisms involving catalytic, radical and condensation reactions.
  • Catalytic mechanism involves metallic species such as iron (Fe), nickel (Ni) and chromium (Cr) which have potential catalytic activity and are used for the inner surface of reactor/cracking coil unit. Filamentous coke is formed with metallic agglomerates at the propagating tips of the unit. These coke filaments are excellent collection sites for cokes formed by various mechanisms including free-radical mechanism and condensation mechanism.
  • Free-radical mechanism involves reactions of micro species, mainly gaseous free radicals, with the macro radicals present at the coke surface, whereas condensation mechanism is a non-catalytic mechanism and occurs at the metallic surface or the coke surface.
  • Heavy poly nuclear compounds present in tar and soot condense at the reactor inner wall and gas interface, where they dehydrogenate and contribute to the coke deposition on the inner walls of the reactor unit.
  • a periodic shut down of the unit is required to burn off the coke by decoking using steam and air at temperatures of around 870°C.
  • decoking is required once in 30-90 days depending on the operation mode and feed composition.
  • the major challenge experienced in steam cracking is reduction of coke deposition in the radiant section and transfer line exchangers (TLE). Efforts are thus required to eliminate or at least reduce coke formation and increase run length between two decokings.
  • the present disclosure relates to a composition comprising alkali metal salt and alkaline metal salts, optionally along with sulfur containing compound, wherein the composition reduces coke formation during hydrocarbon cracking.
  • the composition of the present disclosure further reduces coke formation by memory effect of the composition during hydrocarbon cracking, wherein the memory effect of the composition is retained for at least two cycles of the hydrocarbon cracking.
  • the present disclosure further relates to a method for reducing coke formation during hydrocarbon cracking, wherein the method comprises step of introducing a composition comprising potassium carbonate and calcium acetate, optionally along with sulfur containing compound into a reactor system and subjecting the reactor system to hydrocarbon cracking.
  • Figure 1 relates to a schematic diagram of the experimental set up (pyrolysis system) for thermal cracking process of hydrocarbons and thereby converting it into olefins.
  • Figure 2 relates to a bar chart showing the amount of surface coke formed during hydrocarbon cracking in absence (R-405 and R-408) and presence (R-412) of the composition of the present disclosure.
  • the figure also establishes the sustainable effect of the elements of the composition after primary run, in the form of memory runs Ml and M2 (R-413 and R-414), respectively, demonstrating the memory effect of the composition.
  • Figure 3 relates to a bar chart showing the comparison of percentage reduction in surface coke deposited during hydrocarbon cracking in absence (R-408) and presence (R- 412) of the composition of the present disclosure.
  • the figure also establishes the sustainable effect of the elements of the composition after primary run, in the form of memory runs Ml and M2 (R-413 and R-414), respectively, demonstrating the memory effect of the composition.
  • Figure 4 relates to a bar chart showing the amount of spalled coke formed during hydrocarbon cracking in absence (R-408) and presence (R-412) of the composition of the present disclosure. The figure also establishes the sustainable effect of the elements of the composition after primary run, in the form of memory runs Ml and M2 (R-413 and R-414), respectively, demonstrating the memory effect of the composition.
  • Figure 5 relates to a bar chart depicting the percentage yield of the product yield obtained upon hydrocarbon cracking in in absence (R-408) and presence (R-412) of the composition of the present disclosure.
  • Figure 6 relates to a bar chart depicting the amount of metal leaching recorded by inductively coupled plasma (ICP) analysis during hydrocarbon cracking in absence (R-408) and presence (R-412) of the composition of the present disclosure.
  • ICP inductively coupled plasma
  • the figure also establishes the sustainable effect of the elements of the composition after primary run, in the form of memory runs (R-413 and R-414), respectively, demonstrating the memory effect of the composition.
  • Figure 7 relates to a bar chart showing the amount of metal content observed during hydrocarbon cracking in absence (R-408) and presence (R-412) of the composition of the present disclosure, demonstrating reduced metal leaching by the composition. .
  • the figure also establishes the sustainable effect of the elements of the composition after primary run, in the form of memory runs Ml and Ml (R-413 and R-414), respectively, demonstrating the memory effect of the composition.
  • the present disclosure provides a commercially feasible and inexpensive composition, a method and application of the composition for reducing formation of coke and/or reducing deposition of coke in reactor systems during cracking of hydrocarbon.
  • the present disclosure relates to a composition comprising plurality of inorganic salts, optionally along with sulfur containing compound.
  • the inorganic salts in the composition are metallic salts having same or different cationic and anionic moieties, wherein the cationic moiety includes cations from groups of the Periodic Table including but not limiting to Group IA and Group IIA.
  • the cationic moiety of the composition comprises Group IA metals including but not limiting to lithium, sodium, potassium, rubidium, caesium and francium or Group IIA metals including but not limiting to beryllium, magnesium, calcium, strontium, barium, and radium, or any combination of metals thereof.
  • the anionic moiety of the composition comprises anions including but not limiting to acetate, fumerate, formate, malate, oxalate, carbonates, bicarbonates, sulphates, bisulphates, sulphities and bisulphities.
  • the group IA metal salt in the composition is potassium carbonate.
  • the group 2A metal salt in the composition is calcium acetate.
  • the sulfur containing compound in the composition includes but not limited to dimethyl disulfide (DMDS), dimethyl sulfide (DMS), diethyl sulfide (DES), diethyl disulfide (DEDS), carbon disulfide, dimethyl sulfoxide and a mixture of disulphides.
  • DMDS dimethyl disulfide
  • DMS dimethyl sulfide
  • DES diethyl sulfide
  • DEDS diethyl disulfide
  • carbon disulfide dimethyl sulfoxide and a mixture of disulphides.
  • the concentration of the potassium carbonate and calcium acetate in the composition is ranging from about lppmw to lOOppmw, preferably about lppmw to lOppmw, more preferable about lpppmw to 4ppmw, wherein in the said concentration potassium carbonate is about 30wt% to 40 wt% and calcium acetate is about 60wt% to 70wt%.
  • the concentration of the potassium carbonate and the calcium acetate in the composition is ranging from about lppmw to lOppmw, wherein in the said concentration, potassium carbonate is about 35wt% and calcium acetate is about 65%.
  • the concentration of the potassium carbonate and calcium acetate in the composition is ranging from about lppmw to 4ppmw, wherein in the said concentration, potassium carbonate is about 35wt% and calcium acetate is about 65%.
  • the concentration of the sulfur containing compound in the hydrocarbon feed is ranging from about 50ppmw to 250 ppmw.
  • sulfur is part of the cracking process and the sulfur containing compound is injected as liquid in to the cracking process, alongside the composition of the present disclosure.
  • the sulfur containing compounds include but not limiting to dimethyl disulfide and other disulfides, injected directly into the cracker alongside the composition of the present disclosure.
  • composition of the present disclosure is soluble in solvents including but not limiting to polar solvent and non-polar solvent.
  • the potassium carbonate and calcium acetate of the composition is soluble in water or polar solvents.
  • composition comprising potassium carbonate and calcium acetate, optionally along with sulfur containing compound, of the present disclosure reduces coke formation and/or reduces deposition of coke in a reactor system.
  • composition of the present disclosure reduces coke formation in a reactor system by at least 40%.
  • composition of the present disclosure reduces coke formation in a reactor system by at least 60%.
  • the composition of the present disclosure reduces coke formation in a reactor system during cracking process by at least 40% when compared to the process in absence of the said composition.
  • composition of the present disclosure reduces formation of surface coke during cracking process by at least 60% when compared to the process in absence of the said composition.
  • composition of the present disclosure reduces spalled coke in a reactor system during cracking process by at least 25% when compared to the process in absence of the said composition.
  • composition of the present disclosure demonstrates memory effect, wherein such composition reduces the formation of surface coke by at least 50% and reduces spalled coke by at least 25%, in a reactor system during cracking process.
  • Memory effect represents the composition of the present disclosure remaining after decoking cycle which would reduce coke formation in the subsequent cracking cycle.
  • the composition of the present disclosure added during first cycle of cracking also reduces coke formation in the subsequent cycle, at least for 2 cycles, and there is no need of adding the said composition in the said subsequent cycles of cracking.
  • the memory effect of the composition is retained and is effective for at least 2 cycles of cracking process in the reactor system.
  • composition of the present disclosure in the reactor system during cracking process reduces corrosion by at least 40% when compared to the process in absence of the said composition.
  • composition of the present disclosure in the reactor system during the cracking process reduces metal leaching by at least 50%when compared to the process in absence of the said composition.
  • composition of the present disclosure reduces coke formation within a reactor system, wherein such reactor system includes but is not limited to cracking reactor unit employed for cracking of hydrocarbons.
  • the present disclosure further relates to a method for reducing coke formation and/or deposition of coke during hydrocarbon cracking, said method comprises the step of introducing a reactor system with the composition of the present disclosure.
  • the reactor system includes but is not limited to cracking reactor unit employed for cracking of hydrocarbons.
  • the present disclosure relates to a method of employing the composition of the present disclosure for reducing formation of coke and/or deposition of coke within the reactor system, wherein such reactor system includes but is not limited to cracking reactor unit employed for cracking of hydrocarbons.
  • the method comprises introducing the composition of the present disclosure to said reactor system, wherein the composition comprises potassium carbonate and calcium acetate, optionally along with sulfur containing compound.
  • the method of reducing formation coke and/or deposition of coke within the reactor system during cracking of hydrocarbons comprises steps of:
  • composition of the present disclosure into the reactor system along with water or hydrocarbon feed stock or both;
  • addition of the composition into the reactor system during cracking reduces the formation of surface coke, reduces the formation of spalled coke within the reactor unit, respectively and/or deposition of coke on the inner walls of the reactor unit, transfer lines and cracking tubes within the system employed for the cracking reaction, thereby increasing the run length and reducing the need for frequent decoking of the reactor.
  • the method of the present disclosure employing the composition of the present disclosure results in reduction in coke formation and/or deposition of coke by at least 40% during cracking of hydrocarbon when compared to cracking of hydrocarbons without said composition.
  • the method of the present disclosure employing the composition of the present disclosure results in reduction in coke formation and/or deposition of coke by at least 60% during cracking of hydrocarbon, when compared to cracking of hydrocarbons without said composition.
  • the method of the present disclosure employing the composition of the present disclosure results in reduction of surface coke by at least 60% during cracking of hydrocarbon when compared to cracking of hydrocarbons without said composition.
  • the method of the present disclosure employing the composition of the present disclosure results in reduction of spalled coke by at least 25% when during cracking of hydrocarbon compared to cracking of hydrocarbons without said composition.
  • the composition of the present disclosure demonstrates memory effect, wherein such method having the memory effect of the composition results in reduction of surface coke by at least 50% and results in reduction of spalled coke by at least 25% during hydrocarbon cracking when compared to the hydrocarbon cracking without the composition.
  • the composition of the present disclosure is introduced into the reactor system along with water employed for generation of the steam or along with the steam generated directly or along with the hydrocarbon or hydrocarbon feed stock, or any combination thereof.
  • the composition is injected into the reactor system along with the steam.
  • the composition is injected into the reactor system along with hydrocarbon or hydrocarbon feed stock.
  • the hydrocarbon or the hydrocarbon feed that is loaded into the reactor system includes compounds such as but not limiting to naphtha.
  • the naphtha that is used as the hydrocarbon feed includes but not limited to light naphtha and heavy naphtha, preferably light naphtha.
  • the method of the present disclosure employing the composition of the present disclosure, for reducing formation of coke and/or reducing deposition of coke within reactor system is applicable for any reactor or system conventionally known in the art for cracking of hydrocarbons.
  • Such reactor or system may perform cracking of hydrocarbons by performing a series of steps which are well established and understood by a person skilled in the art.
  • the composition of the present disclosure must be integrated with steps for cracking of hydrocarbons.
  • the method of reducing formation of coke and/or deposition of coke during cracking of hydrocarbons involves the following acts:
  • the temperature of the furnace is lowered to about 20°C, as soon as naphtha is introduced into the reactor due to the endothermic reactions that are occurring in the reactor unit. Thereafter, the temperature is increased slowly to a desired temperature profile of about 450°C to 500°C cross over temperature and coil outlet temperature of about 810°C to 850°C.
  • the product gases that are formed as a result of the reaction are analyzed by using two gas chromatographs.
  • the product gases includes but not limiting to hydrogen, methane, ethane, ethylene, propane, propylene, butane, butenes, 1,2-butadiene, 1,3-butadiene and pentanes.
  • Typical material balance is performed to check the mass conservation, for a predetermined time period by taking the weights of naphtha and water, weighing the amount of liquid product collected, weighing the total amount of gas through gas flow meter during the period and analyzing the product gas so formed.
  • the product gas is analyzed once in about 12 hours.
  • the reactor is cooled down to room temperature of about 20°C to 40°C and weight of thermowell of the reactor is measured to estimate the amount of surface coke reduced during the reaction, wherein the formation of coke is reduced by at least 60%.
  • spalled coke is collected at the end of the run after cooling to room temperature about 20°C to 40°C and opening of the furnace, to estimate the amount of spalled coke reduced during the reaction, wherein the spalled coke is reduced by at least 25%, post which the thermos well is fixed into the reactor followed by which leak test is performed.
  • the method of reducing formation of coke and/or deposition of coke during cracking of hydrocarbons involves the following acts: Initially, the furnace is turned on and the temperature is slowly increased while nitrogen or air is fed in continuously. After a desired temperature profile of about 450°C to 500°C cross over temperature and about 800°C to 830°C of coil outlet temperature is established in the reactor, water is introduced into the reactor unit. After about thirty minutes, nitrogen or air that is supplied is discontinued and hydrocarbon feed (naphtha) along with the composition of the present disclosure is fed into the reactor unit.
  • the flow rates of the naphtha along with the composition of the present disclosure and the water are set in such a way that the desired dilution ratio of about 0.3 to 0.5 is maintained throughout the process.
  • the temperature of the furnace is lowered to about 20°C, as soon as naphtha along with the composition of the present disclosure is introduced into the reactor due to the endothermic reactions that are occurring in the reactor unit. Thereafter, the temperature is increased slowly to a desired temperature profile of about 450°C to 500°C cross over temperature and coil outlet temperature of about 810°C to 850°C.
  • the product gases that are formed as a result of the reaction are analyzed by using two gas chromatographs.
  • Typical material balance is performed to check the mass conservation, for a predetermined time period by taking the weights of naphtha and water, weighing the amount of liquid product collected, weighing the total amount of gas through gas flow meter during the period and analyzing the product gas so formed.
  • the product gas is analyzed once in about 12 hours.
  • the reactor is cooled down to room temperature of about temperature of about 20°C to 40°C and weight of thermowell of the reactor is measured to estimate the amount of surface coke reduced during the reaction, wherein the formation of coke is reduced by at least 60%.
  • spalled coke is collected at the end of the run after cooling to room temperature about 20°C to 40°C and opening of the furnace, to estimate the amount of spalled coke reduced during the reaction, wherein the spalled coke is reduced by at least 25%, post which the thermowell is fixed into the reactor followed by which leak test is performed.
  • the method of the present disclosure employing the composition of the present disclosure involves cracking of hydrocarbons at high temperature ranging from about 800°C to 850°C, preferably at about 825°C.
  • the composition of the present disclosure employed for reducing formation of spalled coke and reducing formation of surface coke within the reactor system and/or deposition of coke on the inner walls of the reactor system comprises potassium carbonate and calcium acetate at concentration ranging from about lppmw to lOOppmw, wherein in the said concentration, potassium carbonate is about 30wt% to 40wt% and calcium acetate is about 60wt% to 70wt% and sulfur containing compound is at a concentration ranging from about 50ppmw to 250 ppmw, with respect to hydrocarbon.
  • the composition of the present disclosure employed for reducing formation of spalled coke and reducing formation of surface coke within the reactor system and/or deposition of coke on the inner walls of the reactor system comprises potassium carbonate and calcium acetate at concentration ranging from about lppmw to lOppmw, wherein in the said concentration, potassium carbonate is about 35wt% and calcium acetate is about 65wt% and sulfur containing compound is at a concentration ranging from about 50ppmwto 250 ppmw, with respect to hydrocarbon.
  • the composition of the present disclosure employed for reducing formation of spalled coke and reducing formation of surface coke within the reactor system and/or deposition of coke on the inner walls of the reactor system comprises potassium carbonate and calcium acetate at concentration ranging from about lppmw to lOppmw, wherein in the said concentration, potassium carbonate is about 35wt% and calcium acetate is about 65wt% and sulfur containing compound is at a concentration ranging from about 50ppmwto 250 ppmw, with respect to hydrocarbon.
  • the metallic salts of the composition decomposes into oxides during the process of hydrocarbon cracking at the pyrolysis temperature of about 810°C to 855°C, which interacts with the coke formed or deposited within the reactor system and catalyses the coke gasification reaction, thereby reducing the net coke formation.
  • the potassium carbonate of the composition decomposes into potassium oxide during the process of hydrocarbon cracking at the pyrolysis temperature of about 810°C to 855°C, said potassium oxide interacts with the coke formed or deposited within the reactor system and catalyses the coke gasification reaction, thereby reducing the net coke formation.
  • the calcium acetate of the composition decomposes into calcium oxide during the process of hydrocarbon cracking at the pyrolysis temperature of about 810°C to 855°C, said calcium oxide interacts with the coke formed or deposited within the reactor system and catalyses the coke gasification reaction, thereby reducing the net coke formation.
  • the sulfur containing compound in the composition controls the excess carbon oxides formed during coke gasification. Thereby acting synergistically along with potassium carbonate and calcium acetate of the composition in reducing coke formation.
  • the sulfur content in the feed and/or in the composition that is used in a reaction should be sufficient to control the excess carbon oxides formed during coke gasification.
  • the relative amount of composition is adjusted to maintain coke reduction and thereby reduce corrosion level.
  • the concentration of each element in the composition is less than 1 ppmw to meet the specifications with respect to fouling and corrosion.
  • ppmw of the composition consists of 65%calcium acetate and 35% of potassium carbonate i.e about 2.6 ppmw of calcium acetate and about 1.4 ppmw of potassium carbonate.
  • the Calcium element concentration in Calcium acetate is about 25% which amounts to about 0.65 ppmw calcium and Potassium element concentration in potassium carbonate is about 56.58% which amounts to about 0.792 ppmw,. Therefore, the concentration of each of the element in the composition is significantly lower than the 1 ppmw limit to minimize the corrosion.
  • FIG. 1 is a representative flow diagram of the pyrolysis system [100] employed for cracking of hydrocarbon feed (naphtha) which comprises naphtha vaporizer, water vaporizer, mixer, cracker furnace, naphtha tank, naphtha feed pump, water feed tank, water feed pump, transfer line heat exchangers (TLEs) 1 and 2 and gas-liquid separator, wherein all the furnaces employed in the system are electrically heated.
  • naphtha which comprises naphtha vaporizer, water vaporizer, mixer, cracker furnace, naphtha tank, naphtha feed pump, water feed tank, water feed pump, transfer line heat exchangers (TLEs) 1 and 2 and gas-liquid separator, wherein all the furnaces employed in the system are electrically heated.
  • naphtha (feed) (10) and water comprising the composition of the present disclosure (12) are stored in two SS tanks at atmospheric pressure.
  • the tanks are provided with level gauges using which the flow rate of the naphtha and water comprising the composition of the present disclosure can be checked regularly.
  • Two tanks are placed on two separate electronic weighing balances (14 and 16) to measure the amount of feed and water comprising the composition consumed in a particular run.
  • the suction is taken from the storage tanks through spiral tube to minimize pulsations in the feed flow.
  • the system further comprises two vaporizers namely naphtha vaporizer (22) and water vaporizer (24) made of SS316. Heat is supplied electrically thereby heating the furnaces to vaporize the naphtha and the water, optionally along with the composition of the present disclosure that is pumped from the metering pumps.
  • the outlets of vaporizers are sent to a mixer (26) where the temperature is raised to a range of about 400°C to 600°C, preferably around 480°C which is referred to as cross over temperature.
  • the reactor coil (36) is a straight tube made of 11 mm inner diameter, 3.01 mm thickness comprising incoloy 800 tube of 355 mm long with a provision to measure temperature profile.
  • Thermowell is 260 mm long and 6.35 mm outer diameter made of SS-316 and fixed from the bottom of the rector tube which also serves as a concentric insert.
  • the coil is fixed in an electrically heated furnace (38) of 360 mm long and 255 mm wide in a single zone. Temperature can be independently controlled to a desired temperature profile of about 450°C to 855°C in the coil at inlet to outlet .
  • Thermocouple is located inside the reactor coil to measure process gas temperature profile by moving the location. The external wall temperature of furnace is measured at center location.
  • the gases that exit from the furnace are quenched to around 600 °C.
  • the naphtha feed flow rate can be varied up to 100 g/h.
  • the gases are further cooled in two transfer line heat exchangers (TLEs 44 & 46) that are connected in series, to condense the steam, optionally comprising the composition of the present disclosure and heaviers in the cracked product mixture.
  • TLEs 44 & 46 transfer line heat exchangers
  • the condensed water and liquid is collected from the gas liquid separator (48) and weighed for mass balance calculations.
  • Non condensed gases are further cooled and measured by a wet gas meter (50).
  • the gaseous mixture is sent for analysis by CO/C02 analyser (52), two Gas Chromatographies (54 & 56) and the output of the GCs goes to Personal Computer for area integration and processing.
  • the cracked gas sample that is liberated after the process is simultaneously analysed by two gas chromatographic (GC) systems. Hydrogen and methane are detected by a thermal conductivity detector (TCD) in the first GC system (HP 3362), whereas all the hydrocarbons present in the gaseous mixture are analysed by second GC (HP 5890) using flame ionisation detector. Peak identification and integration is performed by a commercial integration package and with these identifications, the product distribution in terms of weight percentage can be determined. Since the feed flow rate is known, yields of products %wt/wt of hydrocarbon feed and material balance can be calculated.
  • TCD thermal conductivity detector
  • Example 1 Hydrocarbon cracking with water as steam and without employing the composition of the present disclosure (Control Run) [76] An experimental run (R-405) is carried out in a bench scale cracker having a cracker coil made of Incoloy 800HT and using naphtha as the feed. The coil outlet temperature is maintained at a temperature of about 825°C and steam dilution is at a ratio of about 0.32. The corresponding residence time is around 0.5 seconds. The feed olefin content is found to be about 1.94%. Blank run is carried out using distilled water for steam for a time period of about 48 hours. The surface coke deposited on the surface of thermowell is recorded as 0.26 g at the end of 48 hour run when the furnace is opened after cooling. The reproducibility of the run is tested by repeating the run under same conditions.
  • Example 2 Hydrocarbon cracking with plant steam condensate as water without employing the composition of the present disclosure (Control Run)
  • Example 3 Hydrocarbon cracking in presence of the composition of the present disclosure
  • the amount of surface coke that is formed during the reaction comprising the composition of the present disclosure is reduced by about 60% when compared to benchmark base run performed in Example 2 and as described in Figure 3.
  • the amount of spalled coke is found to be 8.61 grams, which is reduced by about 35% when compared to benchmark base run performed in Example 2, as also described in Figure 4.
  • Further addition of the composition of the present disclosure also did not show any negative effect on product yield, as described in Figures 5 and 6.
  • the components of the final product obtained after the base run of example 2 (without the composition) and the present experiment (with the composition) appear to be very similar in quantity and quality. Further, Inductive Couple Plasma (ICP) analysis of coke and liquid samples that were formed showed no evidence of corrosion, indicating that the composition of the present disclosure does not cause corrosion
  • ICP Inductive Couple Plasma
  • Example 4 Memory effect of the composition of the present disclosure (Trial 1).
  • spalled coke is found to be 9.95g, which is about 25% reduction in spalled coke when compared to the spalled coke formed in blank run of example 2.
  • the reduction of the surface coke and spalled coke in this example is due to the presence of residue elements of the composition of present disclosure that was used in example 3.
  • This memory run is represented by Ml and the results are provided in figures 2 to 4.
  • Example 5 Memory effect of the composition of the present disclosure (Trial 2).
  • An experimental run (R-414) is carried out to further test the memory effect of the residue elements of the composition of the present disclosure left over in the reactor after trial 1 of example 4.
  • This experimental run is carried out under the same conditions as the first memory run as disclosed in example 4.
  • the amount of surface coke that is formed at the end of 48 hour run length is found to be 0.142g, which is about 51% reduction in the surface coke when compared to the surface coke formed in the blank run of Example 2.
  • the amount of spalled coke is found to be 8.52 g, which is about 35.8% reduction in the spalled coke when compared to the spalled coke formed in the blank run of Example 2.
  • ICP Inductive Couple Plasma
  • Element analysis is carried out for all the streams that include bubbler water through which product gas stream is passed, steam condensate, organic liquid product, hydrocarbon feed, aqueous additive solution, TLE wash water, spalled coke, decoking gas and decoking steam condensate, to analyse the effect of elements present in the composition of the present disclosure and where they land up, post completion of the experiments.
  • the results obtained indicate that the elements of the composition land up in the decreasing order in - organic liquid product, spalled coke, steam condensate and decoking steam condensate and, around 1%) of the total elements formed can land up in TLE. Further, the organic liquid stream goes for separation of various products and the elements would be retained in oil and Carbon Black Feed Stock (CBFS).
  • CBFS Carbon Black Feed Stock
  • Thermogravimetric analysis (TGA) of coke sample also show reduced metal content in test runs comprising the composition as disclosed in Figure 7 and thus supporting the observation of reduced metal leaching in test run comprising the composition as reported by ICP analysis. Further, pH of all the samples is found to be within the range as that of the plant in the test run with the composition (R-412) as presented below.
  • the product gases are passed through water in a glass bubbler to dissolve the elements, the sample is noted as BWR.
  • hot water is passed through condenser and collected for analysis which is denoted as TLEW.
  • Sample from steam condensate sent for analysis is called LPRW.
  • Cracker liquid product is extracted with HN03 to extract additive elements in to it which is denoted as ORGW.
  • the present disclosure in view of the above described illustrations and various embodiments, is thus able to successfully overcome the various deficiencies of prior art and provide for an improved process for reducing formation and/or deposition of coke in reactor systems during cracking of hydrocarbons, by employing the composition comprising of metallic salts such as potassium carbonate and calcium acetate, optionally along with sulfur containing compound which decreases the coke formation and/or deposition up to 60% without effecting downstream units.
  • metallic salts such as potassium carbonate and calcium acetate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne une composition comprenant du carbonate de potassium et de l'acétate de calcium, éventuellement avec un composé contenant du soufre. La composition de la présente invention réduit la formation de coke pendant le craquage d'hydrocarbures, réduit en particulier le coke de surface et le coke écaillé pendant le craquage d'hydrocarbures par rapport à un craquage d'hydrocarbures sans ladite composition. L'invention concerne en outre un procédé pour la réduction de la formation et/ou du dépôt de coke pendant la pyrolyse ou le craquage d'hydrocarbures.
PCT/IB2016/054175 2015-07-14 2016-07-13 Compositions, leur procédé et leurs applications Ceased WO2017009785A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/744,405 US20180208856A1 (en) 2015-07-14 2016-07-13 A composition, method and applications thereof
EP16745176.4A EP3322773B1 (fr) 2015-07-14 2016-07-13 Compositions, leur procédé et leurs applications
KR1020187003920A KR20180042849A (ko) 2015-07-14 2016-07-13 조성물, 방법 및 이의 응용

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN2656/MUM/2015 2015-07-14
IN2656MU2015 2015-07-14

Publications (1)

Publication Number Publication Date
WO2017009785A1 true WO2017009785A1 (fr) 2017-01-19

Family

ID=56555505

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2016/054175 Ceased WO2017009785A1 (fr) 2015-07-14 2016-07-13 Compositions, leur procédé et leurs applications

Country Status (4)

Country Link
US (1) US20180208856A1 (fr)
EP (1) EP3322773B1 (fr)
KR (1) KR20180042849A (fr)
WO (1) WO2017009785A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11459513B2 (en) * 2021-01-28 2022-10-04 Saudi Arabian Oil Company Steam cracking process integrating oxidized disulfide oil additive

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5358626A (en) * 1993-08-06 1994-10-25 Tetra International, Inc. Method for retarding corrosion and coke formation and deposition during pyrolytic hydrocarbon procssing
US5567305A (en) * 1993-08-06 1996-10-22 Jo; Hong K. Method for retarding corrosion and coke formation and deposition during pyrolytic hydrocarbon processing
WO1998011174A1 (fr) * 1993-08-06 1998-03-19 Jo Hong K Procede visant a retarder la corrosion et la formation et le depot de coke lors du traitement pyrolytique d'hydrocarbures
US20030183248A1 (en) * 2002-03-28 2003-10-02 Nova Chemicals (International) S.A. Decoke enhancers for transfer line exchangers

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2893941A (en) * 1955-01-27 1959-07-07 Exxon Research Engineering Co Removing and preventing coke formation in tubular heaters by use of potassium carbonate
US4889614A (en) * 1989-05-09 1989-12-26 Betz Laboratories, Inc. Methods for retarding coke formation during pyrolytic hydrocarbon processing
US5463159A (en) * 1994-03-22 1995-10-31 Phillips Petroleum Company Thermal cracking process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5358626A (en) * 1993-08-06 1994-10-25 Tetra International, Inc. Method for retarding corrosion and coke formation and deposition during pyrolytic hydrocarbon procssing
US5567305A (en) * 1993-08-06 1996-10-22 Jo; Hong K. Method for retarding corrosion and coke formation and deposition during pyrolytic hydrocarbon processing
WO1998011174A1 (fr) * 1993-08-06 1998-03-19 Jo Hong K Procede visant a retarder la corrosion et la formation et le depot de coke lors du traitement pyrolytique d'hydrocarbures
US20030183248A1 (en) * 2002-03-28 2003-10-02 Nova Chemicals (International) S.A. Decoke enhancers for transfer line exchangers

Also Published As

Publication number Publication date
EP3322773B1 (fr) 2020-05-13
EP3322773A1 (fr) 2018-05-23
KR20180042849A (ko) 2018-04-26
US20180208856A1 (en) 2018-07-26

Similar Documents

Publication Publication Date Title
Haghighi et al. Investigation of ethylene production in naphtha thermal cracking plant in presence of steam and carbon dioxide
US3291573A (en) Apparatus for cracking hydrocarbons
US5463159A (en) Thermal cracking process
CA2788081A1 (fr) Procedes de production de noir de carbone utilisant une charge d'alimentation prechauffee et appareil a cet effet
SA03230549B1 (ar) طريقة لتحضير اوليفينات منخفضة lower olefines باستخدام تكسير البخار steam cracking
CN102448914A (zh) 用于对分离罐中的原油渣油进行气液分离并使罐底部沉积物再循环的方法和装置
WO2005111175A1 (fr) Procede de craquage thermique d'hydrocarbures
KR100277412B1 (ko) 에틸렌 로 오염방지제
EP3322773B1 (fr) Compositions, leur procédé et leurs applications
US3617479A (en) Suppression of coke and heavy hydrocarbon formation in hydrocarbon units
CN116064093A (zh) 一种重质烃裂解生产烯烃的方法和系统
KR100307155B1 (ko) 열교환표면의코킹을감소시키는방법
RU2110554C1 (ru) Способ и устройство для термической переработки углеводородного сырья
CN101016480A (zh) 一种焦垢抑制剂及其制备方法和应用
WO1997045506A1 (fr) Traitement de tube de craquage pour reduire la formation d'oxyde de carbone et/ou de coke
Parmar et al. Effect of sulfur additives on coke formation during steam cracking of naphtha
Olahova et al. Thermal decomposition of sulfur compounds and their role in coke formation during steam cracking of heptane
Zhang et al. Progress of modern pyrolysis furnace technology
RU2548002C1 (ru) Способ получения этилена из углеводородного сырья
WO2008042083A2 (fr) Construction d'unité de craquage thermique de vaporisation
US20230073862A1 (en) High gas velocity start-up of an ethylene cracking furnace
Salari et al. Investigation of coke deposition & coke inhibition by organosulfur compounds in the pyrolysis of naphtha in the jet stirred reactor system
JPH07242883A (ja) 高沸点炭化水素を熱接触分解するための方法および分解炉
GB1578896A (en) Thermal cracking of hydrocarbons
NL1004705C2 (nl) Werkwijze voor de productie van kleine alkenen.

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: 16745176

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15744405

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20187003920

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2016745176

Country of ref document: EP