US20030111388A1 - Process for catalytic upgrading light petroleum hydrocarbons accompanied by low temperature regenerating the catalyst - Google Patents

Process for catalytic upgrading light petroleum hydrocarbons accompanied by low temperature regenerating the catalyst Download PDF

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Publication number
US20030111388A1
US20030111388A1 US10/156,916 US15691602A US2003111388A1 US 20030111388 A1 US20030111388 A1 US 20030111388A1 US 15691602 A US15691602 A US 15691602A US 2003111388 A1 US2003111388 A1 US 2003111388A1
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United States
Prior art keywords
catalyst
gasoline
light petroleum
process according
oil
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Abandoned
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US10/156,916
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English (en)
Inventor
Ruichi Zhang
Jianguo Ma
Zhili Qin
Jiushun Zhang
Zhijian Da
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
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Assigned to RESEARCH INSTITUTE OF PETROLEUM PROCESSING, CHINA PETROLEUM & CHEMICAL CORPORATION reassignment RESEARCH INSTITUTE OF PETROLEUM PROCESSING ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DA, ZHIJIAN, MA, JIANGUO, QIN, ZHILI, ZHANG, JIUSHUN, ZHANG, RUICHI
Publication of US20030111388A1 publication Critical patent/US20030111388A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/02—Non-metals

Definitions

  • the present invention relates to a catalytic conversion process of petroleum hydrocarbons in the absence of hydrogen, more particularly, a catalytic upgrading process of light petroleum hydrocarbons accompanied by low temperature regenerating the catalyst.
  • U.S. Pat. Nos. 5,043,522 and 5 , 846 , 403 disclose a process for reprocessing gasoline by feeding the catalytic gasoline to the upstream of feeding nozzle of feedstock oil to carry out catalytic conversion of the gasoline by using a regenerated catalyst with a high temperature and a high activity.
  • the yield of light olefins such as propylene, butylene and the like can be increased while the gasoline octane number is raised.
  • CN 1160746A also discloses a catalytic conversion process for increasing gasoline octane number.
  • a gasoline of poor quality such as straight-run gasoline, coking gasoline and the like
  • a reaction temperature 600 to 730° C.
  • a weight hourly space velocity 1 to 180hr ⁇ 1
  • a catalyst-oil ratio 6 to 180.
  • U.S. Pat. No. 5,372,704 discloses a catalytic upgrading process for gasoline by using a spent catalyst.
  • a gasoline cracking rector is added in the conventional catalytic cracking processing flow, and the stripped spent catalyst in contacted with a gasoline fraction that needs to be upgraded in the gasoline cracking reactor, and reacted with each other under the conventional catalytic cracking reaction condition.
  • the reacted catalyst was recycled to a riser reactor and mixed with the regenerated catalyst to carry out the conventional catalytic cracking reaction.
  • the process can increase gasoline octane number and provide some effect to reduce the olefin content in gasoline.
  • An object of the present invention is to provide an effective process for improving the quality of gasoline and/or diesel oil based on the prior art in order to solve the problems of the quality of fuel oils in oil-refining enterprises.
  • the process provided in the present invention comprises: a) introducing the light petroleum hydrocarbons and the regenerated catalyst into a reactor to form a mixture of the feedstock and the catalyst; b) catalytically converting the light petroleum hydrocarbon under the conditions of a temperature of 200 to 450° C., a pressure of 0.1-0.5 Mpa, a catalyst-oil ratio of 2 to 15 and a reaction time of 1 to 20 seconds to form a effluent including gasoline, diesel oil and liquefied gas, and the spent catalyst; c) disengaging the spent catalyst from the effluent; d) stripping the spent catalyst; e) regenerating the stripped spent catalyst for 10 to 50 minutes under a temperature of 400 to 600° C. and a pressure of 0.1 0.6 Mpa; f) feeding the regenerated catalyst back to the reactor for reuse through circulation.
  • the light petroleum hydrocarbon is typically the fraction having a final boiling point of less than 400° C.
  • the process provided in the present invention is suitable for not only in any conventional type of catalytic cracking reactors, such as fluidized beds, risers or down-flow reactors, but also any modified catalytic cracking reactors based on the aforementioned reactors.
  • the essential reaction conditions of the process provided in the present invention are as follows a reaction temperature range from 200 to 450° C., preferably 200 to 400° C. a catalyst-oil ratio of 2 to 15 preferably 3 to 10, a reaction time of 1 to 20 second, preferably 2 to 10 second and a reaction pressure (absolute) range from 0.1 to 0.5 Mpa. Preferably 0.15 to 0.4Mpa.
  • the quantity of atomization steam injected is the same as that in the conventional catalytic cracking process.
  • the weight ratio of atomization steam to light petroleum hydrocarbon is 0.01 to 0.2, preferably 0.02 to 0.05.
  • the stripper suitable for the present invention may be any type of catalytic cracking strippers. Since the stripping temperature of catalyst is relatively low according to the present invention, it should be noted to increase the stripping efficiently. During the procedure of stripper design and operation of the apparatus, the parameters such as stripping time, stripping steam rate, mass flow rate of catalyst in stripper, stripping temperature and the like should be optimized as far as possible. Furthermore, any high efficient stripper or multistage stripper and the like may be selected.
  • Operating conditions of the stripper may be as follows: a stripping temperature of 200 to 450° C., preferably 300 to 400° C., a weight ratio of stripping steam to light petroleum hydrocarbon of 0.005 to 0.05, preferably 0.01 to 0.05, a mass flow rate of 100 to 300 ton/m 2 .hr of catalyst in the stripper, preferably 100 to 200 ton/m 2 .hr, and a stripping time of 0.5 to 10 minutes, preferably 1 to 5 minutes.
  • a lower reaction temperature e.g.
  • overhead steam with a high temperature should be used for stripping so as to increase stripping temperature and improving stripping efficiency; or a part of regenerated catalyst with high temperature may be introduced to the stripper and mixed with the lower temperature spent catalyst in order to increase the stripping temperature therein.
  • the regenerating conditions used in the present invention are much moderate than those in the conventional catalytic cracking process.
  • the regeneration temperature in dense phase is 400 to 600° C., preferably 450 to 550° C.; the regeneration time is 10 to 60 minutes, preferably 10 to 30 minutes, and the regeneration pressure is 0.1 to 0.6Mpa, preferably 0.15 to 0.45Mpa.
  • the content of excess oxygen in regeneration flue gas should be less than 5% by volume, preferably less than 1% by volume.
  • the carbon content of the regenerated catalyst may be controlled at less than 0.7% by weight, preferably less than 0.5% by weight.
  • a cooler for cooling the catalyst may be fitted at downstream of the regenerator to cool a part of or all parts of the regenerated catalyst which is then recycled into the reactor.
  • a nozzle for combustion oil can also be mounted in the regenerator so that the heat balance in the system can be adjusted in a flexible way.
  • the catalyst used in the present invention may be any solid acid catalyst suitable for catalytic cranking process, preferably a catalyst containing high-silicone zeolite with pentasil (pentatomic ring) structure, for example, the catalyst containing ZSM-5 zeolite or ZRP zeolite.
  • the high silicone zeolite may be added during the preparation of the catalyst, or may be prepared alone as an additive containing high silicone zeolite with pentasil structure and added to the catalytic cracking unit.
  • the content of the high silicone zeolite in the catalyst used in the present invention is preferably higher than 2% by weight, more desirably higher than 5% by weight.
  • the catalyst used in the present invention may also contain a Y-type zeolite which is used commonly in the field of catalytic cracking field and a modified zeolite obtained by ion-exchanging or various physico-chemical treatments, for example, HY, REY, REHY, USY, REUSY and the like.
  • the catalyst matrices used in the present invention can be selected from matrices commonly used in catalytic cracking catalysts, such as SiO 2 , Al 2 O 3 , Al 2 O 3 -clay, SiO 2 -clay and the like.
  • one or more additives such as octane number improver, combustion improver, desulfurizer and the like may also be used.
  • the process provided in the present is suitable for employing in different light petroleum hydrocarbons which need to be upgraded or modified, their ASTM distillation ranges may be within the range from an initial boiling point to 400° C., preferably form an initial boiling point to 360° C.
  • the light petroleum hydrocarbon that needs to be upgraded may either be a gasoline and/or diesel oil manufactured by primary processing processes, such as straight-run gasoline, straight-run diesel oil, or a gasoline and/or diesel oil manufactured by secondary processing processes, such as coking gasoline, coking diesel oil, cracking gasoline, cracking light cycle oil, hydrogenated gasoline and the like, or the mixture of the above-mentioned two or more oils.
  • the present invention has the following advantages:
  • the process provided in the present invention depends on a matured catalytic cracking technique by using the continuous reacting and regenerating processes to achieve the catalytic upgrading of light petroleum hydrocarbons. Therefore, the process is simple and easy to be carried out, which needs a little bit change of the conventional catalytic cracking unit.
  • the process provided in the present invention can be used either for improving quality of gasoline fractions such as straight-run gasoline, coking gasoline, cracking gasoline and the like, or for upgrading diesel oil fractions such as cracking light cycle oil, coking diesel oil and the like, or for treating the mixed oils of gasoline and diesel oil.
  • Treating different light petroleum hydrocarbons by using the process provided in the present invention may result in different upgraded effects.
  • a straight-run gasoline is treated with the process of the present invention, its octane number can be increased and its impurity contents of sulfur, nitrogen and the like can be reduced;
  • a cracking gasoline is treated with the process of the present invention, its olefin content and impurity content of sulfur, nitrogen and the like can be decreased;
  • a diesel oil fraction such as cracking light cycle oil, coking diesel oil and the like, is treated with the process of the invention, the content of sulfur and nitrogen therein can be decreased and the freezing point thereof can be lowered.
  • the process provided in the present invention has good selectively to the products and can give more than 90% by weight of the yield of high valuable products.
  • the regeneration of catalyst can be conducted at a lower regeneration temperature, leading to the reduction of the hydrothermal deactivation of the catalyst, and the service life of catalyst can thus be elongated and the consumption of the catalyst running in the unit can also be decreased. Furthermore, owing to a lower regeneration temperature used in the process of the present invention, the requirement for the quality of the material of the regenerator will be lowered during construction of the apparatus, and accordingly the investment in the apparatus construction will be cut down.
  • FIG. 1 is a schematic flow diagram of the process provided in the present invention.
  • a preheated light petroleum hydrocarbon feedstock is fed to a riser reactor 2 via a pipeline 1 , contacted with a regenerated catalyst from a pipeline 15 , and carried out the reaction in the presence of water steam.
  • the reaction oil gas, steam and the deactivated catalyst are subjected to gas/solid phase separation in a disengaging means 7 .
  • the reaction products are transferred to a follow-up separation system via an oil gas pipeline 8 to be further separated into different products.
  • the spent catalyst which accumulates certain quantity of coke falls into a stripper 3 .
  • the steam is introduced into the stripper via a pipeline 4 , after then the spent catalyst is transferred to a regenerator 13 via a pipeline 5 to burn coke deposited on the catalyst.
  • the oxygen-containing gas is introduced to the regenerator 13 via a pipeline 14 ; the flue gas produced by the regeneration enters to a follow-up energy recovery system via a pipeline 12 .
  • the regenerated catalyst which has the carbon content in conformity with the requirement of the present invention, is fed back to the reactor 2 for recycling use.
  • This example illustrates that the quality of the cracking gasoline is improved substantially and can be used for gasoline as a relatively desirable blending component after the gasoline is treated by the process provided in the present invention.
  • the catalyst used in the test was industrially manufactured by the Catalyst Factory of Qi-Lu Petrochemical Corporation with the brand CIP-3, and the main physical-chemical properties were shown in Table 2.
  • the catalyst contained ZRP zeolite and y zeolite.
  • the properties of the catalytic cracking gasoline feedstock used in the test are shown in Table 3.
  • the present example was carried out in a pilot unit which includes the four parts of feeding, reacting, regenerating and fractioning, and had 0.036 ton/day of treatment capacity.
  • this example illustrates that the quality of the coking diesel oil is improved substantially and the coking diesel oil can thus be used as a blending component of diesel oils after the coking diesel oil was treated by the process provided in the present invention.
  • test apparatus, procedure and catalyst used were all the same as those in Example 2.
  • coking diesel oil of pipeline crude oil (of China) was Used as the feedstock, and the properties thereof were shown in Table 4.
  • This example illustrates that the qualities of the gasoline and diesel oil product are improved substantially, and thus the light petroleum hydrocarbon can be used as a blending component of gasoline or diesel oil respectively after the light petroleum hydrocarbon is treated by the process provided in the present invention.
  • a mixed oil of catalytic cracking gasoline and hydrogenation diesel oil was used as a feedstock.
  • the feedstock contained 80% by weight of the cracking gasoline and 20% by weight the hydrogenation diesel oil and the properties of the feedstocks were shown in Table 6.
  • the catalyst used was RMG catalyst (brand) industrially manufactured by Catalyst Factory of Qi-Lu Petrochemical Incorporation, Shandong, China, and the physico-chemical properties thereof were shown in Table 2
  • RMG catalyst containing Y zeolite and ZSM - 5 zeolite is a catalyst for high yield of liquefied gas and gasoline.
  • the fresh RMG catalyst was subjected to steam aging treatment at 760° C. under atmospheric pressure with 100% steam for 8 hours before the test was carried out, the aged catalyst had the micro-activity of 76.

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  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US10/156,916 2001-05-30 2002-05-29 Process for catalytic upgrading light petroleum hydrocarbons accompanied by low temperature regenerating the catalyst Abandoned US20030111388A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNB011184337A CN1179022C (zh) 2001-05-30 2001-05-30 伴有催化剂低温再生的轻质石油烃催化改质方法
CN01118433.7 2001-05-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100236981A1 (en) * 2007-11-09 2010-09-23 Ranfeng Ding System and process for producing high quality gasoline by catalytic hydrocarbon recombination
US20110097673A1 (en) * 2008-04-30 2011-04-28 Ann Forret Chemical looping method for the combustion of heavy liquid hydrocarbon fractions

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20071610A1 (it) * 2007-08-03 2009-02-04 Eni Spa Processo integrato di cracking catalitico fluido per ottenere miscele idrocarburiche con elevate qualita' come carburante
WO2009018722A1 (fr) * 2007-08-09 2009-02-12 China Petroleum & Chemical Corporation Procédé de conversion catalytique
WO2009111953A1 (zh) * 2008-03-13 2009-09-17 中国石油化工股份有限公司 一种从劣质原料油制取轻质燃料油的方法
KR101672789B1 (ko) * 2010-09-27 2016-11-04 차이나 페트로리움 앤드 케미컬 코포레이션 생성물 분포 프로파일을 향상시키기 위한 촉매적 전환 방법
RU2469070C1 (ru) * 2011-10-13 2012-12-10 Учреждение Российской академии наук Институт проблем переработки углеводородов Сибирского отделения РАН (ИППУ СО РАН) Способ переработки бензинов термических процессов и катализатор для его осуществления
US10907110B2 (en) 2016-10-21 2021-02-02 China Petroleum & Chemical Corporation Process for treating gasoline
RU2754030C2 (ru) * 2016-10-21 2021-08-25 Чайна Петролеум Энд Кемикал Корпорейшн Способ очистки бензина
CN111097514B (zh) * 2018-10-29 2022-03-08 中国石油化工股份有限公司 一种低活性加氢改质降凝催化剂活性恢复的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3784463A (en) * 1970-10-02 1974-01-08 Texaco Inc Catalytic cracking of naphtha and gas oil
US5043522A (en) * 1989-04-25 1991-08-27 Arco Chemical Technology, Inc. Production of olefins from a mixture of Cu+ olefins and paraffins
US5154818A (en) * 1990-05-24 1992-10-13 Mobil Oil Corporation Multiple zone catalytic cracking of hydrocarbons
US5270272A (en) * 1992-05-26 1993-12-14 Uop Sulfur removal from molecular-sieve catalyst
US5372704A (en) * 1990-05-24 1994-12-13 Mobil Oil Corporation Cracking with spent catalyst
US5846403A (en) * 1996-12-17 1998-12-08 Exxon Research And Engineering Company Recracking of cat naphtha for maximizing light olefins yields

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3784463A (en) * 1970-10-02 1974-01-08 Texaco Inc Catalytic cracking of naphtha and gas oil
US5043522A (en) * 1989-04-25 1991-08-27 Arco Chemical Technology, Inc. Production of olefins from a mixture of Cu+ olefins and paraffins
US5154818A (en) * 1990-05-24 1992-10-13 Mobil Oil Corporation Multiple zone catalytic cracking of hydrocarbons
US5372704A (en) * 1990-05-24 1994-12-13 Mobil Oil Corporation Cracking with spent catalyst
US5270272A (en) * 1992-05-26 1993-12-14 Uop Sulfur removal from molecular-sieve catalyst
US5846403A (en) * 1996-12-17 1998-12-08 Exxon Research And Engineering Company Recracking of cat naphtha for maximizing light olefins yields

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100236981A1 (en) * 2007-11-09 2010-09-23 Ranfeng Ding System and process for producing high quality gasoline by catalytic hydrocarbon recombination
US8940154B2 (en) * 2007-11-09 2015-01-27 Ranfeng Ding System and process for producing high quality gasoline by catalytic hydrocarbon recombination
US20110097673A1 (en) * 2008-04-30 2011-04-28 Ann Forret Chemical looping method for the combustion of heavy liquid hydrocarbon fractions
US9297528B2 (en) * 2008-04-30 2016-03-29 IFP Energies Nouvelles Chemical looping method for the combustion of heavy liquid hydrocarbon fractions

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RU2276182C2 (ru) 2006-05-10
RU2002114064A (ru) 2004-01-20
CN1179022C (zh) 2004-12-08
CN1388217A (zh) 2003-01-01

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