[go: up one dir, main page]

US20010056216A1 - Optimized process for the preparation of olefins by direct conversion of multiple hydrocarbons - Google Patents

Optimized process for the preparation of olefins by direct conversion of multiple hydrocarbons Download PDF

Info

Publication number
US20010056216A1
US20010056216A1 US09/174,462 US17446298A US2001056216A1 US 20010056216 A1 US20010056216 A1 US 20010056216A1 US 17446298 A US17446298 A US 17446298A US 2001056216 A1 US2001056216 A1 US 2001056216A1
Authority
US
United States
Prior art keywords
catalyst
hydrocarbons
ethane
reactor
hydrocarbon
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.)
Granted
Application number
US09/174,462
Other versions
US6420621B2 (en
Inventor
Yingxun Sha
Zhongqiang Cui
Guoliang Wang
Mingdang Wang
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.)
China Petrochemical Corp
Sinopec Luoyang Guangzhou Engineering Co Ltd
Original Assignee
Sinopec Luoyang Petrochemical Engineering Corp
China Petrochemical Corp
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 Sinopec Luoyang Petrochemical Engineering Corp, China Petrochemical Corp filed Critical Sinopec Luoyang Petrochemical Engineering Corp
Assigned to LUOYANG PETROCHEMICAL ENGINEERING CORPORATION SINOPEC, CHINA PETRO-CHEMICAL CORPORATION reassignment LUOYANG PETROCHEMICAL ENGINEERING CORPORATION SINOPEC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CUI, ZHONGQIANG, SHA, YINGXUN, WANG, GUOLIANG, WANG, MINGDANG
Publication of US20010056216A1 publication Critical patent/US20010056216A1/en
Application granted granted Critical
Publication of US6420621B2 publication Critical patent/US6420621B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06Catalytic processes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04Alumina
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08Silica
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/12Silica and alumina
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04Alkali metals
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00Chemistry of hydrocarbon compounds
    • Y10S585/919Apparatus considerations
    • Y10S585/921Apparatus considerations using recited apparatus structure
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00Chemistry of hydrocarbon compounds
    • Y10S585/919Apparatus considerations
    • Y10S585/921Apparatus considerations using recited apparatus structure
    • Y10S585/922Reactor fluid manipulating device
    • Y10S585/923At reactor inlet

Definitions

  • the present invention relates to a technological process for the preparation of lower olefins with stress on ethylene by conversion of hydrocarbons.
  • the fluidization state of the catalyst in the lift pipe is optimized by installation of special equipment in the pre-lift section of the lift pipe and thereby the contact state of the catalyst and the feed oil for the catalytic cracking in the lift pipe is improved and more ideal product distribution of the catalytic cracking is obtained.
  • Chinese patent ZL 8910052, U.S. Pat. Nos. 5,264,115 and 5,506,365 provide a fluidized bed process and device for converting hydrocarbons which consists of a steam pyrolysis section for light hydrocarbon fractions at the upstream of a reaction zone and a catalytic cracking section for heavy hydrocarbon fractions at the downstream of said reaction zone in a tubular reaction zone with an upstream or downstream flow in the presence of the catalyst particles in a fluidized phase.
  • the applied catalyst belongs to the type of catalytic cracking.
  • the purpose is to obtain a propylene yield slightly higher than the conventional catalytic cracking while raising the yields of gasoline and diesel oil in the product.
  • the major characteristic is to separate C 2 components from the product and then introduce them into an oligomerization reactor to proceed the oligomerization reaction; the remained C 2 components and the oligomerization the catalyst is recycled for reuse after regeneration, different feeds are introduced from different positions, hydrocarbons difficult to pyrolyze are first introduced into the reactor and brought into contact with the catalyst of high temperatures and high activities from the regenerator and the pyrolysis takes place, meanwhile, the catalyst cools down and deactivates; then other hydrocarbons easier to pyrolyze are introduced in sequence from the upstream to downstream of the reaction zone, the hydrocarbons introduced later play a role of quenching those introduced earlier, the temperature of the reaction zone and the activity of the catalyst are lowered step by step from the upstream to the downstream; the positions from which various hydrocarbons enter the
  • Another aspect of the present invention is to provide a process for direct conversion of heavy hydrocarbons to produce lower olefins with stress on ethylene and co-produce light aromatics, which is to bring the hydrocarbon feeds into contact with a solid granular catalyst in a piston flow reactor to proceed catalytic pyrolysis, the feed hydrocarbons are mixed with steam and introduced, the general reaction conditions in the reaction zone are: temperature 600-900° C., pressure 0.13-0.40 MPa (absolute), total steam/hydrocarbon ratio 0.1-1.0, total catalyst/oil ratio 5-100 and the catalyst/oil contact time 0.02-5 s; the oil gas after reaction is separated quickly from the catalyst and quenched, the catalyst is recycled for reuse after regeneration; the oil gas enters a fractionation and separation system to proceed the separation, a product gas mainly containing ethylene, the by-product ethane, and a liquid product rich in aromatics can be obtained, the highly pure by-product ethane from the separation system and/or the gases containing
  • the catalyst cools down and deactivates, steam is introduced at the same time when ethane feed is introduced from the upstream inlet of the reactor; heavy hydrocarbon feeds are introduced at position certain distance from downstream of the inlet for ethane, the hydrocarbons introduced later play a role of quenching those introduced earlier, the reaction temperature at this moment is lowered to 680-800° C.; the feeding positions of the by-product ethane and the heavy hydrocarbons are determined as such that the residence time of ethane, which is difficult to pyrolyze, is long, while that of heavy hydrocarbons, which are easy to pyrolyze, is short, the differences in the residence times of ethane and heavy hydrocarbons in the reactor are 0.01-3 s.
  • FIG. 1 Schoematic diagram of the lift pipe reactor of the present invention as an example
  • Hydrocarbons entering the reactor from different inlets are subjected to different reaction conditions, for light hydrocarbons, which are difficult to pyrolyze, the pyrolysis temperature is higher and the pyrolysis time is longer, while for heavy hydrocarbons, which are difficult to pyrolyze, the reaction temperature is lower and the pyrolysis time is shorter. Hydrocarbons with different properties are fed to the reactor in sequence and the differences in the residence times in the reactor of adjacent hydrocarbons are 0.0-3 s.
  • Hydrocarbons hard to pyrolyze are first fed to the reactor and brought into contact with the catalyst of high temperatures and high activities from the regenerator and the pyrolysis reaction takes place, at the same time, the catalyst cools down and deactivates and then other hydrocarbon feeds easy to pyrolyze are fed in sequence, the hydrocarbons fed later play a role of quenching those fed earlier.
  • This method is usable for the technology in which one or multiple hydrocarbon oil(s) are used as the feed(s), said hydrocarbons include ethane, propane, butane, light hydrocarbons and heavy hydrocarbons.
  • Said heavy hydrocarbons are referred to the hydrocarbons with a distillation range higher than 350° C., including straight run heavy hydrocarbons and secondary processing heavy hydrocarbons, i.e., various straight run wax oils, coker wax oils, straight run vacuum gas oils, atmospheric residues, coker gas oils, thermal cracking heavy oils, solvent-deasphalted oils and various solvent extraction residues of heavy hydrocarbons;
  • said light hydrocarbons are referred to hydrocarbons with a distillation range lower than 350° C., such as LPG, refinery petroleum gases, oil field gases, oil field light hydrocarbons, naphtha and light diesel oil.
  • the particular process is described as follows (see FIG. 1): the regenerated catalyst 4 from the regenerator enters the lift pipe 1, and then flows upward under the driving of the pre-lifting steam and pre-lifting dry gas introduced from the bottom of the lift pipe; the pre-lifting dry gas is highly pure ethane from the separation zone of the pyrolyzed gas and/or light hydrocarbon gases of other sources containing ethane, steam is added at the same time; ethane quickly pyrolyzes under the action of the hot catalyst at 780-900° C., ethane may also be sprayed from inlet I.
  • a mixture of propane and/or butane from the separation zone and/or other sources and a certain amount of steam is atomized and sprayed from feed inlet II into the lift pipe, where the mixture comes into contact with the mixed stream of the catalyst and the ethane reactant at about 780-850° C. and the catalytic pyrolysis reaction takes place.
  • a mixture of the light hydrocarbons having a distillation range lower than 350° C. and a certain amount of steam is atomized and sprayed from feed inlet II into the lift pipe, where the mixture comes into contact with the mixture of the catalyst and the upstream reactants at 720-830° C. and the catalytic pyrolysis reaction takes place.
  • the mixture of the catalyst and the reaction stream of the hydrocarbon feeds in the lift pipe flows upward and enters the subsider 3, wherein fast separation of gas/solid stream is performed.
  • the reaction stream is removed from the outlet 6 at the top of the subsider, while the deactivated catalyst drops down along the subsider and is stripped by the stripping steam sprayed from the pipeline 5.
  • the stripped catalyst to be regenerated goes down and enters the regenerator, wherein the coke-burning regeneration reaction is carried out, the regeneration temperature being 700-950° C.
  • the catalyst absorbs a great amount of heat and its temperature rises to 800-900° C.
  • the high temperature regenerated catalyst is recycled back to the pre-lift section of the lift pipe along the regeneration inclined pipe for reuse.
  • the reaction stream removed from exit 6 enters the fractionation system and separates into pyrolyzed gas and a liquid product rich in aromatics, the pyrolyzed gas is then separated in the separation system into highly pure individual hydrocarbons (CH 4 , C 2 H 4 , C 2 H 6 , C 3 H 6 , C 3 H 8 , C 4 H 8 , C 4 H 6 , C 4 H 10 ), wherein the highly pure ethane returns to be bottom of the lift pipe for pyrolysis or is delivered to the ethane pyrolysis heater for pyrolysis.
  • highly pure individual hydrocarbons CH 4 , C 2 H 4 , C 2 H 6 , C 3 H 6 , C 3 H 8 , C 4 H 8 , C 4 H 6 , C 4 H 10
  • the components of the special catalyst (LCM) used for the catalytic pyrolysis can be selected from SiO 2 , Al 2 O 3 and oxides of alkali metals, alkali earth metals and transition metals or mixtures thereof, aluminum silicate modified with oxides of alkali or alkali earth metals can also be used, and optionally, a part of molecular sieves are added.
  • feed hydrocarbon to be pyrolyzed are two or more in the scope of ethane, propane, butane, light hydrocarbons having a distillation range lower than 350° C. and heavy hydrocarbons having a distillation range higher than 350° C., different feeds can enter the device from different positions according to the above method to realize the optimization of the pyrolysis conditions.
  • This example is the pyrolysis results using an atmospheric residue and ethane as a co-feed.
  • the pyrolysis test is carried out on a high-low parallel lift pipe pilot-scale device with a total length of the lift pipe being 15 . 42 m, its internal diameter being 19 mm and a capacity being 0.24 t/d.
  • Ethane which is difficult to pyrolyze, is first introduced into the lift pipe from the bottom of the lift pipe and brought into contact with the hot and active regenerated catalyst so that reaction takes place, the temperature of the regenerated catalyst at this moment is 820° C., the temperature of the hydrocarbon/catalyst mixture after introducing ethane is 810° C.
  • the inlet of the atmospheric residue is located 4.2 m above the inlet of ethane.
  • the residence time of ethane from the bottom to this point is 0.45 s.
  • the temperature of the mixed stream after introducing the atmospheric residue is 740° C.
  • the temperature at the outlet of the lift pipe is 710° C.
  • the catalyst used in this example is numbered as LCM-A, its properties and composition are shown in Table 1.
  • the process conditions and the material balance in a pilot-scale test of the lift pipe are shown in Table 2. For comparison, the result of the pilot-scale test is also shown when the atmospheric residue and ethane is mixed and fed from the same inlet.
  • This example is the pyrolysis results using an atmospheric residue and a straight run gasoline as a co-feed, the process conditions and the material balance in a pilot-scale test of the lift pipe are shown in Table 3.
  • the straight run gasoline is introduced into the device from the bottom of the lift pipe, the number of the catalyst used is LCM-B, its propertied and composition are seen in Table 1.
  • the temperature of the catalyst/oil mixture is 780° C.
  • the atmospheric residue is sprayed at the position 4.2 m above the inlet of the straight run gasoline
  • the residence time of the straight run gasoline from the bottom to this point is 0.6 s
  • the temperature of the mixed stream after spraying the atmospheric reside is 700° C.
  • the temperature at the outlet of the lift pipe is 660° C.

Landscapes

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

Abstract

A process for hydrocarbon conversion to prepare lower olefins such as ethylene, propylene, etc., and light aromatics by bringing hydrocarbons into contact with a solid granular catalyst. In order to optimize the reaction conditions and product structure and save the capital and operating costs, a piston flow reactor is used in this process and multiple groups of feed inlets, which allow hydrocarbons with different properties to enter the device from different feed inlets and proceed pyrolysis under different operation conditions, are set on the reactor. This process is usable for individual pyrolysis or co-feed pyrolysis of hydrocarbons from refinery gases, liquid hydrocarbons, to heavy residues.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a technological process for the preparation of lower olefins with stress on ethylene by conversion of hydrocarbons. [0001]
  • BACKGROUND ARTS
  • Research on the production of ethylene by the pyrolysis of heavy oils has been very active in recent years both in china and abroad, for example, the QC (quick contact) reaction system developed by Stone & Webster Eng Co. of USA (U.S. Pat. No. 4,663,019, ZL88102644.1 and EP 0381870A etc.): this technology uses a downward tubular reactor and a feeding mode of a single feed oil. The steam pyrolysis technology developed by British Petroleum Ltd. (U.S. Pat. No. 4,087,350): this technology uses a tubular fixed bed catalytic reactor. The technology developed by Tokyo Science and Technology Co. of Japan for producing olefins using coke particles as a heat carrier (U.S. Pat. No. 4,259,177): this technology uses a fluidized bed reactor of the reaction-regeneration type. The HCC (Heavy-oil contact cracking) technology developed by SINOPEC Loyang Petro-Chemical Engineering Co. (ZL 92105507.2): this technology uses an up flow or down flow tubular piston flow reactor and a feeding mode of a single feed oil. The above technologies are all able to produce ethylene from heavy oils. But in the flow sheets of the above technologies, only the case of feeding a single fresh feed oil is considered. American patent U.S. Pat. No. 5,348,644 is patent for an invention relating to the improvement of the feeding equipment and technological process of a lift pipe catalytic cracking device. The fluidization state of the catalyst in the lift pipe is optimized by installation of special equipment in the pre-lift section of the lift pipe and thereby the contact state of the catalyst and the feed oil for the catalytic cracking in the lift pipe is improved and more ideal product distribution of the catalytic cracking is obtained. Chinese patent ZL 8910052, U.S. Pat. Nos. 5,264,115 and 5,506,365 provide a fluidized bed process and device for converting hydrocarbons which consists of a steam pyrolysis section for light hydrocarbon fractions at the upstream of a reaction zone and a catalytic cracking section for heavy hydrocarbon fractions at the downstream of said reaction zone in a tubular reaction zone with an upstream or downstream flow in the presence of the catalyst particles in a fluidized phase. The applied catalyst belongs to the type of catalytic cracking. The purpose is to obtain a propylene yield slightly higher than the conventional catalytic cracking while raising the yields of gasoline and diesel oil in the product. The major characteristic is to separate C[0002] 2 components from the product and then introduce them into an oligomerization reactor to proceed the oligomerization reaction; the remained C2 components and the oligomerization the catalyst is recycled for reuse after regeneration, different feeds are introduced from different positions, hydrocarbons difficult to pyrolyze are first introduced into the reactor and brought into contact with the catalyst of high temperatures and high activities from the regenerator and the pyrolysis takes place, meanwhile, the catalyst cools down and deactivates; then other hydrocarbons easier to pyrolyze are introduced in sequence from the upstream to downstream of the reaction zone, the hydrocarbons introduced later play a role of quenching those introduced earlier, the temperature of the reaction zone and the activity of the catalyst are lowered step by step from the upstream to the downstream; the positions from which various hydrocarbons enter the reactor are determined as such that the residence times of various hydrocarbons in the reactor are gradually decreased in the sequence from difficulty to ease in pyrolysis, the differences in the residence times of every adjacent two hydrocarbon feeds in the reactor are 0.01-3 s.
  • Another aspect of the present invention is to provide a process for direct conversion of heavy hydrocarbons to produce lower olefins with stress on ethylene and co-produce light aromatics, which is to bring the hydrocarbon feeds into contact with a solid granular catalyst in a piston flow reactor to proceed catalytic pyrolysis, the feed hydrocarbons are mixed with steam and introduced, the general reaction conditions in the reaction zone are: temperature 600-900° C., pressure 0.13-0.40 MPa (absolute), total steam/hydrocarbon ratio 0.1-1.0, total catalyst/oil ratio 5-100 and the catalyst/oil contact time 0.02-5 s; the oil gas after reaction is separated quickly from the catalyst and quenched, the catalyst is recycled for reuse after regeneration; the oil gas enters a fractionation and separation system to proceed the separation, a product gas mainly containing ethylene, the by-product ethane, and a liquid product rich in aromatics can be obtained, the highly pure by-product ethane from the separation system and/or the gases containing ethane from other sources return to the pyrolysis reactor of the piston flow type from the upstream inlet of the reactor and come into contact with the catalyst of high temperatures and high activities, fast pyrolysis takes place at temperatures higher than 780° C. to produce ethylene and meanwhile, the catalyst cools down and deactivates, steam is introduced at the same time when ethane feed is introduced from the upstream inlet of the reactor; heavy hydrocarbon feeds are introduced at position certain distance from downstream of the inlet for ethane, the hydrocarbons introduced later play a role of quenching those introduced earlier, the reaction temperature at this moment is lowered to 680-800° C.; the feeding positions of the by-product ethane and the heavy hydrocarbons are determined as such that the residence time of ethane, which is difficult to pyrolyze, is long, while that of heavy hydrocarbons, which are easy to pyrolyze, is short, the differences in the residence times of ethane and heavy hydrocarbons in the reactor are 0.01-3 s.[0003]
  • BRIEF DESCRIPTION OF THE DRAWING
  • FIG. 1—Schematic diagram of the lift pipe reactor of the present invention as an example [0004]
  • 1-Lift pipe [0005]
  • 2-Pre-lift gas [0006]
  • 3-Subsider [0007]
  • 4-Regenerated catalyst [0008]
  • 5-Pipeline for stripping steam [0009]
  • 6-Outlet of the pyrolyzed gas [0010]
  • I, II, III, IV are all the feed inlets[0011]
  • DETAILED DESCRIPTION OF THE INVENTION
  • Hydrocarbons entering the reactor from different inlets are subjected to different reaction conditions, for light hydrocarbons, which are difficult to pyrolyze, the pyrolysis temperature is higher and the pyrolysis time is longer, while for heavy hydrocarbons, which are difficult to pyrolyze, the reaction temperature is lower and the pyrolysis time is shorter. Hydrocarbons with different properties are fed to the reactor in sequence and the differences in the residence times in the reactor of adjacent hydrocarbons are 0.0-3 s. Hydrocarbons hard to pyrolyze are first fed to the reactor and brought into contact with the catalyst of high temperatures and high activities from the regenerator and the pyrolysis reaction takes place, at the same time, the catalyst cools down and deactivates and then other hydrocarbon feeds easy to pyrolyze are fed in sequence, the hydrocarbons fed later play a role of quenching those fed earlier. [0012]
  • This method is usable for the technology in which one or multiple hydrocarbon oil(s) are used as the feed(s), said hydrocarbons include ethane, propane, butane, light hydrocarbons and heavy hydrocarbons. Said heavy hydrocarbons are referred to the hydrocarbons with a distillation range higher than 350° C., including straight run heavy hydrocarbons and secondary processing heavy hydrocarbons, i.e., various straight run wax oils, coker wax oils, straight run vacuum gas oils, atmospheric residues, coker gas oils, thermal cracking heavy oils, solvent-deasphalted oils and various solvent extraction residues of heavy hydrocarbons; said light hydrocarbons are referred to hydrocarbons with a distillation range lower than 350° C., such as LPG, refinery petroleum gases, oil field gases, oil field light hydrocarbons, naphtha and light diesel oil. [0013]
  • Citing a lift pipe reactor as an example, the particular process is described as follows (see FIG. 1): the [0014] regenerated catalyst 4 from the regenerator enters the lift pipe 1, and then flows upward under the driving of the pre-lifting steam and pre-lifting dry gas introduced from the bottom of the lift pipe; the pre-lifting dry gas is highly pure ethane from the separation zone of the pyrolyzed gas and/or light hydrocarbon gases of other sources containing ethane, steam is added at the same time; ethane quickly pyrolyzes under the action of the hot catalyst at 780-900° C., ethane may also be sprayed from inlet I. A mixture of propane and/or butane from the separation zone and/or other sources and a certain amount of steam is atomized and sprayed from feed inlet II into the lift pipe, where the mixture comes into contact with the mixed stream of the catalyst and the ethane reactant at about 780-850° C. and the catalytic pyrolysis reaction takes place. A mixture of the light hydrocarbons having a distillation range lower than 350° C. and a certain amount of steam is atomized and sprayed from feed inlet II into the lift pipe, where the mixture comes into contact with the mixture of the catalyst and the upstream reactants at 720-830° C. and the catalytic pyrolysis reaction takes place. A mixture of heavy hydrocarbons having a distillation range higher than 350° C. and a certain amount of steam is atomized and sprayed from feed inlet IV into the lift pipe, where the mixture comes into contact with the mixture of the catalyst and the upstream reaction stream at about 680-800° C. and the catalytic pyrolysis reaction takes place. The distances among the feed inlets for various hydrocarbons are calculated to allow the differences in the residence time of the adjacent hydrocarbons introduced into the reactor in sequence to be 0.0-3 s. Heavier feed oils are sprayed in sequence into the lift pipe at the inlets above the inlets from which the lighter feed oils are sprayed and may play a role of quenching the pyrolyzed stream of lighter feed oils so that the secondary reactions of the pyrolyzed stream of the lighter feed oils are quickly stopped or slowed down. The mixture of the catalyst and the reaction stream of the hydrocarbon feeds in the lift pipe flows upward and enters the subsider 3, wherein fast separation of gas/solid stream is performed. The reaction stream is removed from the outlet 6 at the top of the subsider, while the deactivated catalyst drops down along the subsider and is stripped by the stripping steam sprayed from the pipeline 5. The stripped catalyst to be regenerated goes down and enters the regenerator, wherein the coke-burning regeneration reaction is carried out, the regeneration temperature being 700-950° C. During the coke-burning regeneration, the catalyst absorbs a great amount of heat and its temperature rises to 800-900° C. After steam stripping in the transfer pipeline, the high temperature regenerated catalyst is recycled back to the pre-lift section of the lift pipe along the regeneration inclined pipe for reuse. After quenching, the reaction stream removed from exit 6 enters the fractionation system and separates into pyrolyzed gas and a liquid product rich in aromatics, the pyrolyzed gas is then separated in the separation system into highly pure individual hydrocarbons (CH4, C2H4, C2H6, C3H6, C3H8, C4H8, C4H6, C4H10), wherein the highly pure ethane returns to be bottom of the lift pipe for pyrolysis or is delivered to the ethane pyrolysis heater for pyrolysis.
  • The components of the special catalyst (LCM) used for the catalytic pyrolysis can be selected from SiO[0015] 2, Al2O3 and oxides of alkali metals, alkali earth metals and transition metals or mixtures thereof, aluminum silicate modified with oxides of alkali or alkali earth metals can also be used, and optionally, a part of molecular sieves are added.
  • If the feed hydrocarbon to be pyrolyzed are two or more in the scope of ethane, propane, butane, light hydrocarbons having a distillation range lower than 350° C. and heavy hydrocarbons having a distillation range higher than 350° C., different feeds can enter the device from different positions according to the above method to realize the optimization of the pyrolysis conditions. [0016]
  • The effect of the present invention. Realization of the pyrolysis of the feeds with different properties under different process conditions results in the optimization of the reaction conditions and product structure, e.g., the yield of ethylene attains 23.76 wt % or higher, as well as savings of capital and operating costs. [0017]
  • EXAMPLE 1
  • This example is the pyrolysis results using an atmospheric residue and ethane as a co-feed. The pyrolysis test is carried out on a high-low parallel lift pipe pilot-scale device with a total length of the lift pipe being [0018] 15.42 m, its internal diameter being 19 mm and a capacity being 0.24 t/d. Ethane, which is difficult to pyrolyze, is first introduced into the lift pipe from the bottom of the lift pipe and brought into contact with the hot and active regenerated catalyst so that reaction takes place, the temperature of the regenerated catalyst at this moment is 820° C., the temperature of the hydrocarbon/catalyst mixture after introducing ethane is 810° C. The inlet of the atmospheric residue is located 4.2 m above the inlet of ethane. The residence time of ethane from the bottom to this point is 0.45 s. The temperature of the mixed stream after introducing the atmospheric residue is 740° C., the temperature at the outlet of the lift pipe is 710° C. The catalyst used in this example is numbered as LCM-A, its properties and composition are shown in Table 1. The process conditions and the material balance in a pilot-scale test of the lift pipe are shown in Table 2. For comparison, the result of the pilot-scale test is also shown when the atmospheric residue and ethane is mixed and fed from the same inlet.
  • The results in Table 2 show that, in the technology of ethylene production from atmospheric residues with ethane re-refining, rather optimal pyrolysis conditions for both the atmospheric residue and ethane are realized and the conversions are appropriate when the method of multiple feed at separate point of the present invention are adopted. The yield of ethylene from the individual pyrolysis of the atmospheric residue is 22.36 wt %, while that after the re-refining of 4.56% of ethane attains 25.63 wt %. [0019]
  • It can also be seen from Table 2 that when the pyrolyzed ethane from the atmospheric residue is not re-refined and additional 6.5 wt % ethane is added, if ethane and the heavy oil are fed from the same feed inlet and the temperature of catalyst/oil mixture is 740° C., the yield of ethylene is only 21.30%; if ethane and the heavy oil are fed into the device from different feed inlets, i.e., the temperature at the inlet for ethane is 810° C. and that for the residue is 740° C., the yield of ethylene is 23.76%. Moreover, the aromatic content in the pyrolyzed gasoline is greater than 86 wt %, that in the pyrolyzed liquid product having a distillation range higher than 200° C. is greater than 89 wt %. [0020]
  • EXAMPLE 2
  • This example is the pyrolysis results using an atmospheric residue and a straight run gasoline as a co-feed, the process conditions and the material balance in a pilot-scale test of the lift pipe are shown in Table 3. The straight run gasoline is introduced into the device from the bottom of the lift pipe, the number of the catalyst used is LCM-B, its propertied and composition are seen in Table 1. The temperature of the catalyst/oil mixture is 780° C., the atmospheric residue is sprayed at the position 4.2 m above the inlet of the straight run gasoline, the residence time of the straight run gasoline from the bottom to this point is 0.6 s, and the temperature of the mixed stream after spraying the atmospheric reside is 700° C., the temperature at the outlet of the lift pipe is 660° C. [0021]
  • The results in Table 3 show that, by using the method of mixed feed of the atmospheric residue and the straight run gasoline, the total pyrolysis extent of the mixed feed is rather low when the optimal conditions for the pyrolysis of the atmospheric residue are ensured, in the total material balance, the yields of ethylene and propylene are 21.84% and Z12.93%, respectively, either of them is lower than that when only the atmospheric reside is pyrolyzed, indicating that the pyrolysis extent of the straight run gasoline is not high; rather high pyrolysis extent of the straight run gasoline is attained while ensuring that the pyrolysis of the atmospheric residue proceeds under the optimal conditions by using the method of the multiple feed at separate point of the present invention: in the total material balance of the mixed feed, the yield of ethylene reaches 24.50%, that of propylene reaches 14.51%, either of them exceeds that when only the atmospheric residue is pyrolyzed. [0022]
  • Table 1 Properties and composition of the catalyst [0023]
    TABLE 1
    Properties and composition of the catalyst
    Catalyst LCM-A Catalyst LCM-B
    Item Alkali Transition metal
    Type of the active component earth metal Oxides oxides
    Chemical
    composition
    Al2O3, wt % 40 42
    Na2O, wt % <0.3 <0.3
    Fe2O3, wt % 0.8 0.8
    Active component, wt % 8.2 6.5
    Specific surface, m2/g 58 65
    Porosity, ml/g 0.12 0.13
    Bulk density, g/ml 0.85 0.85
    Sieve composition, wt %
     0-20 μ 2.6 3.2
    20-40 μ 19.4 20.2
    40-60 μ 31.5 32.1
    60-80 μ 24.7 23.9
    >80 μ 21.8 20.6
  • Table 2 Pyrolysis result using ethane and an atmospheric residue [0024]
    TABLE 2
    Pyrolysis result using ethane and an atmospheric residue
    Material balance Material balance
    for the pyrolysis for the pyrolysis
    of the atmospheric of the atmospheric
    Item residue residue and ethane
    Feeding mode Single Separate* Mixed Separate
    Whether ethane is refined No Yes No No
    Ethane content in feed, wt % 0.0 0.0 6.5 6.5
    Temp. of regeneration 820 820 820 820
    bed, ° C.
    Temp. of stripping steam for 400 400 400 400
    regenerated catalyst, ° C.
    Stream temp. after spraying / 810 740 810
    ethane, ° C.
    Stream temp. after spraying 740 740 740 740
    atmospheric residue, ° C.
    Temp. at the outlet of lift 710 710 710 710
    pipe, ° C.
    Temp. after quenching, ° C. 600 600 600 600
    Catalyst type A A A A
    Steam/hydrocarbon ratio, 0.23 0.23 0.23 0.23
    wt/wt
    Catalyst/oil ratio, wt/wt 18.0 18.0 18.0 10
    Yield of major products, wt %
    Hydrogen 0.87 1.09 0.84 1.03
    Methane 11.44 11.81 10.76 11.13
    Ethylene 22.36 25.63 21.30 23.76
    Ethane 4.56 / 10.20 6.79
    Propylene 12.86 13.25 12.05 12.21
    Propane 0.71 0.72 0.67 0.68
    Butane 0.22 0.22 0.21 0.21
    Butylene 3.04 3.10 2.85 2.90
    Butadiene 1.87 1.91 1.75 1.76
    Pyrolyzed gasoline (<200° C.) 12.46 12.76 11.68 11.85
    Pyrolyzed middle distillate 5.23 5.24 4.94 4.89
    Pyrolyzed heavy oil 9.86 9.88 9.30 9.22
    (>300° C.)
    Coke 13.23 13.27 12.40 12.37
    Loss 1.29 1.12 1.05 1.21
    Where: (1) Aromatic content 88.12 87.75 86.54 87.87
    in pyrolyzed gasoline
    (2) Aromatic content in the 90.13 89.89 90.10 91.39
    pyrolyzed product having a
    distillation range higher than
    200° C.
  • *: Ethane in the pyrolyzed product from the atmospheric residue is returned back to the lift pipe for re-refining. [0025]
  • Table 3 Pyrolysis result using straight run gasoline and an atmospheric residue [0026]
    TABLE 3
    Pyrolysis result using straight run gasoline and an atmospheric residue
    Material balance Material balance Material balance for
    for the pyrolysis for pyrolysis of pyrolysis of
    of atmospheric straight run atmospheric residue and
    Item residue gasoline straight run gasoline
    Feeding mode Single Single Mixed Separate
    Gasoline proportion in feed, wt % 0.0 100 20 20
    Temp. of regeneration bed, ° C. 800 / 800 800
    Temp. of stripping steam for regenerated 400 / 400 400
    catalyst, ° C.
    Stream temp. after spraying gasoline, ° C. / 780 700 780
    Stream temp. after spraying atmospheric residue, ° C. 700 700 700 700
    Temp. at the outlet of the lift pipe, ° C.
    Temp. after quenching, ° C. 660 660 660 660
    Catalyst type 600 600 600 600
    Steam/hydrocarbon ratio, wt/wt B B B B
    Catalyst/oil ratio, wt/wt 0.25 / 0.25 0.25
    18.6 / 19.2 19.0
    Yield of major products, wt %
    Ethylene 23.05 30.30 21.84 24.50
    Propylene 14.01 16.51 12.93 14.51
    C4 olefins 6.73 8.48 6.24 7.08
    Pyrolyzed gasoline (<200° C.) 13.45 19.20 23.16 14.60
    Pyrolyzed middle distillate 6.60 2.00 5.50 5.68
    Pyrolyzed heavy oil (>300° C.) 9.31 0.01 7.45 7.45
    Coke plus loss 9.00 0.50 7.30 7.30
    Where: (1) Aromatic content in pyrolyzed 88.44 92.30 78.52 89.10
    gasoline
    (2) Aromatic content in the pyrolyzed product 92.65 / 92.50 93.76
    having a distillation range higher than 200° C.

Claims (11)

1. A process for catalytic pyrolysis of hydrocarbon feeds to produce lower olefins with stress on ethylene and co-produce light aromatics, in which the hydrocarbon feeds are brought into contact with a solid granular catalyst in a piston flow reactor to proceed catalytic pyrolysis, the hydrocarbon feeds including two or more hydrocarbons having different physicochemical properties, the feed hydrocarbons being mixed with steam and introduced, the general reaction conditions in the reaction zone being: temperature 600-900° C., pressure 0.13-0.40 MPa (absolute), total steam/hydrocarbon ratio 0.1-1.0, total catalyst/oil ratio 5-100 and the catalyst/oil contact time 0.02-5 s; the oil gas after reaction is separated quickly from the catalyst and quenched, the catalyst is recycled for reuse after regeneration; different feeds are introduced from different positions, hydrocarbons difficult to pyrolyze are first introduced into the reactor and brought into contact with the catalyst of high temperatures and high activities from the regenerator and the pyrolysis takes place, meanwhile, the catalyst cools down and deactivates; other hydrocarbons easier to pyrolyze are introduced in sequence from the upstream to downstream of the reaction zone, the hydrocarbons introduced later play a role of quenching those introduced earlier, the temperature of the reaction zone and the activity of the catalyst are lowered step by step from the upstream to the downstream; the positions from which various hydrocarbons enter the reactor are determined as such that the residence times of various hydrocarbons in the reactor are gradually decreased in the sequence from difficulty to ease in pyrolysis, the differences in the residence times of every adjacent two hydrocarbon feeds in the reactor are 0.0-3 s.
2. A process according to
claim 1
, wherein the hydrocarbon feeds having different physicochemical properties include ethane, propane, butane, light hydrocarbons with a distillation range lower than 350° C., and heavy hydrocarbons with a distillation range higher than 350° C.
3. A process according to
claim 2
, wherein the light hydrocarbons with a distillation range lower than 350° C. include LPG, refinery petroleum gases, oil field gases, oil field light hydrocarbons, naphtha and light diesel oil; the heavy hydrocarbons with a distillation range higher than 350° C. include straight run and secondary processing heavy hydrocarbons, i.e., straight run wax oils, coker wax oils, straight run vacuum gas oils, atmospheric residues, coker gas oils, thermal cracking heavy oils, solvent-deasphalted oils and various residues from solvent extraction of heavy hydrocarbons.
4. A process according to
claim 2
, wherein the controlled temperature ranges for various hydrocarbons are: ethane, 780-900° C.; propane and/or butane, 750-850° C.; the light hydrocarbons with a distillation range higher lower than 350° C., 720-830° C.; and the heavy hydrocarbons with a distillation range higher than 350° C., 680-800° C.
5. A process according to
claim 3
or
4
, wherein the two hydrocarbon feeds are ethane and atmospheric residues respectively.
6. A process according to
claim 1
-4, wherein the components of the pyrolysis catalyst used can be selected from SiO2, Al2O3 and oxides of alkali metals, alkali earth metals and transition metals or mixtures thereof, aluminum silicate modified with oxides of alkali or alkali earth metals can also be used, and optionally, a part of molecular sieves are added.
7. A process according to
claim 1
, wherein, the deactivated catalyst is delivered to the regenerator for regeneration by burning off the coke after stream stripping; the regeneration temperature is 750-950° C., the high temperature regenerated catalyst is drawn after steam stripping and recycled back to the reactor through the inclined pipe for reuse.
8. A process for direct conversion of heavy hydrocarbon to produce lower olefins with stress on ethylene and co-produce light aromatics, in which the hydrocarbon feed is bought into contact with a solid granular catalyst in a piston flow reactor to proceed catalytic pyrolysis, the feed hydrocarbon is mixed with steam and introduced, the general reaction conditions in the reaction zone are: temperature 660-900° C., pressure 0.13-0.40 MPa (absolute), total steam/hydrocarbon ratio 0.1-1.0, total catalyst/oil ratio 5-100 and the catalyst/oil contact time 0.02-5 s; the oil gas after reaction is separated quickly from the catalyst and quenched, the catalyst is recycled for reuse after regeneration; the oil gas enters a fractionation and separation system to proceed the separation, a product gas mainly containing ethylene, the by-product ethane, and a liquid product rich in aromatics can be obtained; the highly pure by-product ethane from the separation system and/or the gases containing ethane from other sources return to the pyrolysis reactor of the piston flow type from the upstream inlet of the reactor and come into contact with the catalyst of high temperatures and high activities, fast pyrolysis takes place at temperatures higher than 780° C. to produce ethylene and meanwhile, the catalyst cools down and deactivates, steam is introduced at the same time when ethane feed is introduced from the upstream inlet of the reactor; heavy hydrocarbon feed is introduced at position certain distances from downstream of the inlet for ethane, the hydrocarbon introduced later play a role of quenching those introduced earlier, the reaction temperature at this moment is lowered to 680-800° C.; the feeding positions of the by-product ethane and the heavy hydrocarbon are determined as such that the residence time of ethane, which is difficult to pyrolyze, is long, while that of heavy hydrocarbon, which are easy to pyrolyze, is short, the differences in the residence times of ethane and heavy hydrocarbons in the reactor are 0.0-3 s.
9. A process according to
claim 8
, wherein the heavy hydrocarbon is the hydrocarbon having a distillation range higher than 350° C., including straight run heavy hydrocarbons and secondary processing heavy hydrocarbons, i.e., straight run wax oils, coker wax oils, straight run vacuum gas oils, atmospheric residues, coker gas oils, thermal cracking heavy oils, solvent-deasphalted oils and various residues from solvent extraction of heavy hydrocarbons.
10. A process according to
claim 8
or
9
, wherein the components of the catalyst used for pyrolysis can be selected from SiO2, Al2O3 and oxides of alkali metals, alkali earth metals and transition metals or mixtures thereof, aluminum silicate modified with oxides of alkali or alkali earth metals can also be used, and optionally, a part of molecular sieves are added.
11. A process according to
claim 8
or
9
, wherein the deactivated catalyst is delivered to the regenerator for regeneration by burning off the coke after stream stripping, the regeneration temperature is 750-950° C., the high temperature regenerated catalyst is drawn after stripping and recycled back to the reactor through the inclined pipe for reuse.
US09/174,462 1997-10-20 1998-10-19 Optimized process for the preparation of olefins by direct conversion of multiple hydrocarbons Expired - Lifetime US6420621B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN97119048A CN1056595C (en) 1997-10-20 1997-10-20 Process for direct-conversion preparation olefines from multiple fed hydrocarbon
CNCN97119048.8 1997-10-20
CN97119048A 1997-10-20

Publications (2)

Publication Number Publication Date
US20010056216A1 true US20010056216A1 (en) 2001-12-27
US6420621B2 US6420621B2 (en) 2002-07-16

Family

ID=5175152

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/174,462 Expired - Lifetime US6420621B2 (en) 1997-10-20 1998-10-19 Optimized process for the preparation of olefins by direct conversion of multiple hydrocarbons

Country Status (4)

Country Link
US (1) US6420621B2 (en)
EP (1) EP0911308B1 (en)
CN (1) CN1056595C (en)
DE (1) DE69809685T2 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110240523A1 (en) * 2008-12-10 2011-10-06 Sukumar Mandal fluid catalytic cracking (fcc) process for manufacturing propylene and ethylene in increased yield
RU2464298C2 (en) * 2007-08-09 2012-10-20 Чайна Петролеум & Кемикал Корпорейшн Method for catalytic conversion (versions)
US9242909B2 (en) 2008-12-26 2016-01-26 Jx Nippon Oil & Energy Corporation Method for refining dicyclopentadiene
US9993620B2 (en) 2013-06-28 2018-06-12 Safesharp Technologies Corporation Catheter anchoring device and method
CN110724550A (en) * 2018-07-16 2020-01-24 中国石油化工股份有限公司 A kind of method and system for catalytic cracking using fast fluidized bed
CN112973579A (en) * 2021-02-07 2021-06-18 中国科学院过程工程研究所 Gas-solid short contact time reaction device and application thereof

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4412886B2 (en) * 2001-08-29 2010-02-10 中國石油化工股▲分▼有限公司 Catalytic cracking of petroleum hydrocarbons
US6867341B1 (en) 2002-09-17 2005-03-15 Uop Llc Catalytic naphtha cracking catalyst and process
US20050085677A1 (en) * 2003-10-15 2005-04-21 Fina Technology, Inc. Method for improved production of cyclohexenyl and alkenyl aromatic compounds
CN100487080C (en) * 2004-03-08 2009-05-13 中国石油化工股份有限公司 Chemical oil-refining method for preparing low carbon olefin and arene
WO2005085391A1 (en) * 2004-03-08 2005-09-15 China Petroleum & Chemical Corporation A process of production of lower olefins and aromaticas
US7560020B2 (en) * 2006-10-30 2009-07-14 Exxonmobil Chemical Patents Inc. Deasphalting tar using stripping tower
CN101362959B (en) * 2007-08-09 2012-09-05 中国石油化工股份有限公司 Catalytic conversion method for preparing propone and high-octane number gasoline
CN101362669B (en) * 2007-08-09 2012-12-12 中国石油化工股份有限公司 Catalytic conversion method of ethylene, propylene and aromatic hydrocarbon preparation
CN101760227B (en) * 2008-12-25 2013-06-05 中国石油化工股份有限公司 Catalytic conversion method for preparing propylene and high octane gasoline
US9458390B2 (en) * 2009-07-01 2016-10-04 Exxonmobil Chemical Patents Inc. Process and system for preparation of hydrocarbon feedstocks for catalytic cracking
CN102811814B (en) 2010-01-20 2014-10-15 吉坤日矿日石能源株式会社 Catalyst for use in production of monocyclic aromatic hydrocarbon, and process for production of monocyclic aromatic hydrocarbon
US9181146B2 (en) 2010-12-10 2015-11-10 Exxonmobil Chemical Patents Inc. Process for the production of xylenes and light olefins
CN108947938A (en) 2011-01-24 2018-12-07 国际壳牌研究有限公司 The preparation method of ethylene oxide
US9067901B2 (en) 2011-01-24 2015-06-30 Shell Oil Company Process for the production of ethylene oxide
JP5690624B2 (en) 2011-03-25 2015-03-25 Jx日鉱日石エネルギー株式会社 Monocyclic aromatic hydrocarbon production method
US8921633B2 (en) 2012-05-07 2014-12-30 Exxonmobil Chemical Patents Inc. Process for the production of xylenes and light olefins
US9181147B2 (en) 2012-05-07 2015-11-10 Exxonmobil Chemical Patents Inc. Process for the production of xylenes and light olefins
US8937205B2 (en) 2012-05-07 2015-01-20 Exxonmobil Chemical Patents Inc. Process for the production of xylenes
WO2014129585A1 (en) 2013-02-21 2014-08-28 Jx日鉱日石エネルギー株式会社 Method for producing single-ring aromatic hydrocarbons
US9896627B2 (en) * 2015-10-14 2018-02-20 Saudi Arabian Oil Company Processes and systems for fluidized catalytic cracking
US10767117B2 (en) 2017-04-25 2020-09-08 Saudi Arabian Oil Company Enhanced light olefin yield via steam catalytic downer pyrolysis of hydrocarbon feedstock
US10870802B2 (en) 2017-05-31 2020-12-22 Saudi Arabian Oil Company High-severity fluidized catalytic cracking systems and processes having partial catalyst recycle
US10889768B2 (en) 2018-01-25 2021-01-12 Saudi Arabian Oil Company High severity fluidized catalytic cracking systems and processes for producing olefins from petroleum feeds
US11066606B2 (en) 2019-11-12 2021-07-20 Saudi Arabian Oil Company Systems and methods for catalytic upgrading of vacuum residue to distillate fractions and olefins with steam
US11066605B2 (en) 2019-11-12 2021-07-20 Saudi Arabian Oil Company Systems and methods for catalytic upgrading of vacuum residue to distillate fractions and olefins
US11434432B2 (en) 2020-09-01 2022-09-06 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking of a greater boiling point fraction with steam
US11332680B2 (en) 2020-09-01 2022-05-17 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking of lesser and greater boiling point fractions with steam
US11230672B1 (en) 2020-09-01 2022-01-25 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking
US11352575B2 (en) 2020-09-01 2022-06-07 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize hydrotreating of cycle oil
US11505754B2 (en) 2020-09-01 2022-11-22 Saudi Arabian Oil Company Processes for producing petrochemical products from atmospheric residues
US11230673B1 (en) 2020-09-01 2022-01-25 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking of a lesser boiling point fraction with steam
US11242493B1 (en) 2020-09-01 2022-02-08 Saudi Arabian Oil Company Methods for processing crude oils to form light olefins

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1493888A (en) 1975-09-25 1977-11-30 British Petroleum Co Olefins production
US4291185A (en) * 1978-12-14 1981-09-22 Mobil Oil Corporation Alkylation of benzene in petroleum
JPS585225B2 (en) 1978-12-21 1983-01-29 工業技術院長 Method of heating coke particles
US4242100A (en) * 1979-10-15 1980-12-30 Tri-Pak, Inc. Motor fuel composition
US4320241A (en) * 1980-08-28 1982-03-16 Occidental Research Corporation Process for converting oxygenated hydrocarbons into hydrocarbons
US4422925A (en) * 1981-12-28 1983-12-27 Texaco Inc. Catalytic cracking
US4670021A (en) * 1983-01-10 1987-06-02 Texaco Inc. Detergent and corrosion inhibiting additive and motor fuel composition containing same
US4663019A (en) 1984-03-09 1987-05-05 Stone & Webster Engineering Corp. Olefin production from heavy hydrocarbon feed
US4693991A (en) * 1986-05-02 1987-09-15 Phillips Petroleum Company Hydrotreating catalyst composition
FR2625509B1 (en) * 1987-12-30 1990-06-22 Total France METHOD AND DEVICE FOR CONVERTING HYDROCARBONS INTO A FLUIDIZED BED
US5264115A (en) 1987-12-30 1993-11-23 Compagnie De Raffinage Et De Distribution Total France Process and apparatus for fluidized bed hydrocarbon conversion
US5173174A (en) * 1988-07-07 1992-12-22 Uop Metal-tolerant FCC catalyst and process
DE68906529T2 (en) 1989-02-08 1993-09-23 Stone & Webster Eng Corp METHOD FOR PRODUCING OLEFINS.
FR2654435B1 (en) * 1989-11-10 1992-03-13 Total France METHOD AND APPARATUS FOR CONTACTING A HYDROCARBON LOAD WITH HOT SOLID PARTICLES IN A TUBULAR REACTOR WITH AN ASCENDING FLUIDIZED BED.
JP2966985B2 (en) * 1991-10-09 1999-10-25 出光興産株式会社 Catalytic hydrotreating method for heavy hydrocarbon oil
CN1030313C (en) * 1992-07-16 1995-11-22 中国石油化工总公司 Method for preparing ethylene by directly converting heavy hydrocarbon

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2464298C2 (en) * 2007-08-09 2012-10-20 Чайна Петролеум & Кемикал Корпорейшн Method for catalytic conversion (versions)
US20110240523A1 (en) * 2008-12-10 2011-10-06 Sukumar Mandal fluid catalytic cracking (fcc) process for manufacturing propylene and ethylene in increased yield
US8685232B2 (en) * 2008-12-10 2014-04-01 Reliance Industries Limited Fluid catalytic cracking (FCC) process for manufacturing propylene and ethylene in increased yield
US9242909B2 (en) 2008-12-26 2016-01-26 Jx Nippon Oil & Energy Corporation Method for refining dicyclopentadiene
US9783469B2 (en) 2008-12-26 2017-10-10 Jx Nippon Oil & Energy Corporation Method for refining dicyclopentadiene
US9993620B2 (en) 2013-06-28 2018-06-12 Safesharp Technologies Corporation Catheter anchoring device and method
CN110724550A (en) * 2018-07-16 2020-01-24 中国石油化工股份有限公司 A kind of method and system for catalytic cracking using fast fluidized bed
CN112973579A (en) * 2021-02-07 2021-06-18 中国科学院过程工程研究所 Gas-solid short contact time reaction device and application thereof

Also Published As

Publication number Publication date
EP0911308A1 (en) 1999-04-28
DE69809685T2 (en) 2003-04-10
CN1056595C (en) 2000-09-20
JPH11193250A (en) 1999-07-21
CN1215041A (en) 1999-04-28
US6420621B2 (en) 2002-07-16
EP0911308B1 (en) 2002-11-27
DE69809685D1 (en) 2003-01-09
JP3953208B2 (en) 2007-08-08

Similar Documents

Publication Publication Date Title
US6420621B2 (en) Optimized process for the preparation of olefins by direct conversion of multiple hydrocarbons
US11306258B2 (en) Enhanced light olefin yield via steam catalytic downer pyrolysis of hydrocarbon feedstock
KR100281750B1 (en) Method and apparatus for preparing low molecular weight olefins
US10167434B2 (en) Integrated hydrocracking process
CN110540869B (en) A method of catalytic cracking
CN101323798B (en) Catalytic conversion method and special apparatus therefor
US9162955B2 (en) Process for pyrolysis of a coal feed
CN114540069A (en) Method and device for preparing olefin by cracking petroleum hydrocarbon and application
US4828681A (en) Process of thermally cracking hydrocarbons using particulate solids as heat carrier
EP4219664A1 (en) Method and device for producing low-carbon olefins and btx by catalytically cracking hydrocarbon-containing raw oil
US5220093A (en) Process for production of olefins from mixtures of light paraffins
EP1713884B1 (en) Method for selective component cracking to maximize production of light olefins
CN104557395A (en) Catalytic conversion method for production of propylene
CN115992005B (en) Reaction method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by catalytic conversion of hydrocarbon raw material as reaction raw material
CN115992003B (en) Method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by catalytic conversion of hydrocarbon raw material as reaction raw material
CN115992006B (en) Reaction method and reactor for preparing low-carbon olefin and aromatic hydrocarbon by fluidization catalytic conversion of hydrocarbon raw material as reaction raw material
JP3953208B6 (en) Optimized olefin production process by direct conversion of multiple hydrocarbons
TW202237804A (en) Fluidized catalytic conversion method for producing low-carbon olefins from hydrocarbons
CN115895710B (en) Catalytic conversion method and device for producing low-carbon olefin
CN116376591B (en) Method and device for co-producing low-carbon olefins and high-octane gasoline from Fischer-Tropsch synthesis products
TWI899361B (en) Method and device for producing light olefins and BTX by catalytic cracking of hydrocarbon-containing raw oil
CN114606021B (en) Method and system for producing ethylene and propylene
CN200985320Y (en) Device for cracking hydrocarbon oil
CN118028021A (en) A method and system for producing light olefins by catalytic cracking of petroleum hydrocarbons
CN119528672A (en) A method for preparing light olefins

Legal Events

Date Code Title Description
AS Assignment

Owner name: LUOYANG PETROCHEMICAL ENGINEERING CORPORATION SINO

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SHA, YINGXUN;CUI, ZHONGQIANG;WANG, GUOLIANG;AND OTHERS;REEL/FRAME:009675/0495

Effective date: 19981217

Owner name: CHINA PETRO-CHEMICAL CORPORATION, CHINA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SHA, YINGXUN;CUI, ZHONGQIANG;WANG, GUOLIANG;AND OTHERS;REEL/FRAME:009675/0495

Effective date: 19981217

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12