WO2004072002A1 - Procede de production d'olefine inferieure - Google Patents

Procede de production d'olefine inferieure Download PDF

Info

Publication number
WO2004072002A1
WO2004072002A1 PCT/JP2004/000676 JP2004000676W WO2004072002A1 WO 2004072002 A1 WO2004072002 A1 WO 2004072002A1 JP 2004000676 W JP2004000676 W JP 2004000676W WO 2004072002 A1 WO2004072002 A1 WO 2004072002A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
raw material
propylene
ethylene
reaction
Prior art date
Application number
PCT/JP2004/000676
Other languages
English (en)
Japanese (ja)
Inventor
Phala Heng
Michiaki Umeno
Teruo Muraishi
Toshihiro Takai
Original Assignee
Mitsui Chemicals, Inc.
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 Mitsui Chemicals, Inc. filed Critical Mitsui Chemicals, Inc.
Priority to JP2004544182A priority Critical patent/JP4335144B2/ja
Publication of WO2004072002A1 publication Critical patent/WO2004072002A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation 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
    • C07C4/06—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a process for producing lower-order olefins, particularly ethylene and propylene, from a raw material by catalytically cracking a 4- to 12-carbon olefin using a catalyst.
  • Ethylene and propylene are important substances as basic raw materials for various chemicals and resins.
  • these olefins are obtained by thermal or catalytic decomposition in naphtha crackers, but their production ratio is around 1: 0.6, which is the source of the difference between the supply and demand of ethylene or propylene. It has become. Therefore, in recent years, a method for selectively obtaining propylene from a hydrocarbon material containing C4 to C12 olefins, which are components of low utility such as butene and pentene, has become important. Many methods are known for catalytically converting these hydrocarbon raw materials containing 4 to 12 olefins using a zeolite catalyst.
  • European Patent No. 1 909 59 states that butene is catalytically cracked using Proton-type ZSM-5 zeolite (another name for MFI zeolite) to produce propylene.
  • a method is disclosed. The process describes reaction conditions of low reaction temperatures at 400 and 500 and a high feed rate per unit weight of catalyst (WHSV) of 60 hr- 1 or more.
  • the raw material butene concentration used in this method 1 0 0% and high and, for low and S i O 2 / A 1 2 0 3 molar ratio of 2 8 Zeorai bets catalyst used, but the description is not However, under these conditions, the amount of coke generated is large, and therefore the activity of the catalyst decreases rapidly, so that it cannot be used for a long time.
  • European Patent No. 1,090,600 discloses a method for producing propylene by catalytic decomposition of butene using a protonated silica light. Subsequent studies revealed that the silicalite used in this method was a zeolite having an MFI type zeolite structure. However, the raw material butene concentration used in this method is as high as 100%, and the catalyst activity decreases rapidly under the conditions of high feed rate per unit weight of catalyst (WHSV), which provides high productivity. . Also described in Example, the reaction conditions of low temperature 5 0 0 catalyst for a long time can be used, per unit weight of the catalyst feeding rate of (WH SV) is 6 hr 1 and low and therefore the propylene and Echiren Low productivity.
  • WHSV high feed rate per unit weight of catalyst
  • U.S. Pat.No. 5,981,181 discloses a process for producing propylene using pentasil-type zeolite under the following low-reaction temperature conditions at 500 in the presence of water in the raw material. Is disclosed. However, with this method, the feed rate of raw material per unit weight of catalyst (WH SV) is as low as 1 to 3 hr1, and high propylene and ethylene productivity cannot be obtained.
  • WH SV feed rate of raw material per unit weight of catalyst
  • Japanese Patent Application Laid-Open Publication No. Hei 6-73332 discloses an example of proton type ZSM-5.
  • the reaction temperature is as high as 600 X: a large amount of coke is deposited, equivalent to 6 OOP PM based on the total weight of the supplied raw materials. Is described in the Examples, and it is expected that the catalyst activity decreases rapidly when used in a fixed bed.
  • Japanese Unexamined Patent Publication No. Hei 11 — 2464445 (corresponding to WO9928905), Japanese Unexamined Patent Publication No. Hei11-24669 (Japanese Patent No. Japanese Patent Application Laid-Open No. H11-246680 (corresponding to WO9928980), Japanese Patent Application Laid-Open No. H11-246981 (W09929) No. 804), Japanese Patent Application Laid-Open No. H11 — 2464872 (WO 9292980)
  • Japanese Unexamined Patent Application Publication No. 06 Japanese Unexamined Patent Application Publication No. 11-26639 (corresponding to WO992907), Japanese Unexamined Patent Application Publication No. 11-266710 (WO9) 9 2 9 4 2 1), Japanese Unexamined Patent Publication No.
  • Patent Application Laid-Open No. 2000-41069 corresponds to WO078894
  • European Patent 1 195 542 No. 4 discloses a method for producing a product containing ethylene and propylene by catalytically cracking a hydrocarbon feedstock containing olefins using proton-type MFI zeolite.
  • the gen compound in the raw material is reduced by hydrogenation treatment to suppress the decrease in the activity.
  • the amount of the gen compound in the raw material is 0.5 wt%, the activity of propylene is not stable. Over time (Comparative Example 4, page 16 and FIG. 8, page 38).
  • the present invention uses a zeolite catalyst to catalytically crack a hydrocarbon containing 4 to 12 carbon atoms to form a lower molecular weight material mainly composed of ethylene and propylene.
  • a zeolite catalyst to catalytically crack a hydrocarbon containing 4 to 12 carbon atoms to form a lower molecular weight material mainly composed of ethylene and propylene.
  • by-products such as hydrogen, saturated hydrocarbons, aromatic hydrocarbons, and coke are suppressed, and coke precipitates on the catalyst even in raw materials containing relatively large amounts of gen compounds.
  • An object of the present invention is to provide a method for producing ethylene and propylene selectively and with high productivity while suppressing the deterioration of the catalyst over a long period of time. Disclosure of the invention
  • the present inventors have intensively studied to solve the above problems. As a result, we have developed a production technology that exhibits high ethylene and propylene selectivity, low coke accumulation, which can be expected for long catalyst life, and high productivity.
  • This manufacturing technology was created as a result of studying the catalytic cracking reaction mechanism, which had not been systematically studied. That is, the mechanism of the reaction for producing ethylene and propylene from carbon atoms having 4 to 12 carbon atoms is significantly different from those of carbon atoms having 4 carbon atoms (butene). That is, in the case of an olefin having more than 4 carbon atoms, a carpocation is generated at an acidic active site of the catalyst, and a lower carbon olefin is generated by breaking a carbon-carbon bond.
  • butene it can be explained as follows with reference to the mechanism of isolemination of olefin reported in Applied Catalysis A: General 206 (2001) 57-66. That is, in the case of butene, octene is first formed by dimerization, and becomes propylene and pentene via a more stable secondary carpocation. This reaction proceeds rapidly because the reaction intermediate is stable. The resulting pentene then decomposes, yielding ethylene and propylene, but the reaction is slow because the primary primary force lipocation is used to produce ethylene. Further, the present inventors have studied using a computational chemistry technique, and have obtained results supporting this estimation.
  • the raw material contains at least one kind of carbon having 4 to 12 carbon atoms, and contains 10 to 70 wt% of at least one kind of carbon having 1 to 12 saturated hydrocarbons.
  • the feed rate (WH SV) per unit weight of catalyst (WH SV) is 32 to 25 under the reaction pressure of 0.05 to 2 MPa.
  • FIG. 1 shows the changes over time in butene conversion, ethylene and propylene yield in Examples 9, 10 and 1.
  • a graph connecting diamonds represents Example 9, a graph connecting squares represents Example 10, and a graph connecting a circle represents Example 1.
  • the top graph shows the conversion of the putene, the middle graph shows the propylene yield, and the bottom graph shows the ethylene yield.
  • BEST MODE FOR CARRYING OUT THE INVENTION the raw material contains at least one or more carbon atoms of 4 to 12 olefins, and contains 10 to 70 wt% of at least one or more carbon atoms of 1 to 12 saturated hydrocarbons.
  • Ethylene and propylene can be selectively obtained mainly from the olefin component by catalytic cracking of a contained raw material using a catalyst.
  • the present inventors have surprisingly found that by using such a mixed raw material of olefin and saturated hydrocarbon, the generation of coke is suppressed, and the decrease in catalytic activity is suppressed. Furthermore, they have found that even with a raw material containing a relatively large amount of a gen compound, the deposition of coke on the catalyst is suppressed, and a decrease in catalyst activity is suppressed. Also, even if hydrogen is contained in the raw materials used, coke generation can be similarly suppressed. In this case, the value of the partial pressure of hydrogen is preferably in the range of 0.1 to 0.9.
  • the starting material used has 4 to 12 carbon atoms, for example, 1-butene, cis-1-butene, trans-1-butene, isobutene, 1-pentene, cis-1-pentene , Trans-1-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-11-butene, cyclopentene, 1-1hexene, 2-hexene, 3-hexene, methylbutenes, dimethyl Butenes, neohexene, cyclohexene, methylcyclopentene, linear heptene, branched heptene, cyclic heptene, methylcyclohexene, C9-C12 linear, branched, or cyclic Olefins.
  • the content of the saturated hydrocarbon having 1 to 12 carbon atoms in the raw material used is 10 to 70 wt%, preferably 10 to 60 wt%, more preferably 20 to 20 wt%. Expressed as ⁇ 50wt%. Under the conditions of the present invention, substantially no such conversion of saturated hydrocarbons occurs, but surprisingly, if the content of these saturated hydrocarbons in the feedstock used is below this range, the activity of the catalyst is reduced. Be faster.
  • hydrocarbons 1 to 12 carbon atoms
  • hydrocarbons include methane, ethane, propane, n-butane, isobutane, linear, branched and cyclic pentane, linear, branched and cyclic, hexane, linear, branched and cyclic heptane, linear and branched And cyclic octane.
  • aromatic hydrocarbons such as benzene, toluene and xylene may be contained.
  • the gen compound contained in the raw material used in accordance with the present invention is a hydrocarbon gen having 3 to 12 carbon atoms, such as propagene, 1,2-butadiene, 1,3-butadiene, 1,2-pentadiene, 1,3-Penyugen, 1,4-Penyugen, 2,3-Penyugen, 1,2-Hexagen, 1,3-Hexagen, 1,4-Hexagen, 1,5-Hexagen , 2,3-hexadiene, 2,4-hexadiene, 1,2-heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene , 2,3-Heptadiene, 2,4-Heptogen, 2,5-Heptogen, 3,4-Heptogen, 1,2-Octadien, 1,3-Octogen, 1 , 4-Octadien, 1,5-Octadien, 1,6-Oc
  • Examples of the raw material having such a component include a naphtha pyrolysis furnace or a distillate obtained from the top of a debutane tower sent after separating a C1 to C3 fraction from a mixture obtained in a naphtha catalytic cracking furnace.
  • a fraction obtained by extracting and removing isoprene from a fraction (a C5 fraction of a cloud), or the entire amount thereof is selectively catalytically hydrogenated without extracting an isoprene from a C5 fraction of a crude to reduce the gen component.
  • Off-line distillation with wt% or less Butadiene disolen is extracted from the fraction obtained from the top of the depentanizer sent after separating the C1 to C3 fraction from the mixture obtained in the naphtha pyrolysis furnace or the naphtha catalytic cracking furnace.
  • an orefin fraction in which the total amount is selectively catalytically hydrogenated to reduce the gen component to 2 wt% or less.
  • raw materials may be used alone, or may be used as a mixture in an arbitrary amount.
  • the raw materials are not limited to those described above, and may be those containing at least one kind of saturated hydrocarbons having 4 to 12 carbon atoms and 10 to 70 wt% of at least one carbon atom. Any material can be used.
  • an MFI type zeolite catalyst is used as the catalyst used in the present invention. S i 0 2 / A 1 2 0 3 molar ratio of Zeorai Bok until 5 0 0 0 beyond normal .1 2 0, preferably 2 0 0 5 0 0 0, more preferably 2 8 0 5 0 0 0 And particularly preferably 280 000.
  • the molar ratio S i 0 2 / A 1 2 ⁇ 3 is lower than this, the catalytic activity is too high, so that the coke deposition rate is high in the temperature range where the decomposition reaction is thermodynamically favorable, Is not preferred because of its stability when repeatedly used.
  • the molar ratio of SiO 2 / A 12 O 3 is higher than this range, the number of active points decreases, and it is not preferable because the active point can no longer function as an acid catalyst.
  • MF I type Zeorai DOO catalyst may be used as a commercial product having a S i ⁇ 2 ZA 1 2 O 3 molar ratio of purpose, a known method by the Zeorai bets composition deviating these ranges as a starting material It is also possible to obtain by That is, a commercial product having a low SiO 2 SZAlz O 3 molar ratio can be dealuminated and converted to a higher silica zeolite. Examples of the method for dealumination are described in Catalysis and Zeolites, Fundamentals and Applications J. Weitkamp, .Puppe Hi Collection, Springer, 1999, 1 271 155, steam treatment, treatment with silicon tetrachloride, Hexaful mouth silicate treatment and the like can be mentioned.
  • MFI zeolite products contain sodium or ammonium as a cation, but any of them can be used in the present invention if the following treatment is performed. That is, the zeolite exchanged with the ammonium cation is converted, for example, to a proton type by treating it at 500 with 5 hours, and then used as a catalytic cracking reaction catalyst.
  • those having an alkali metal ion such as sodium are stirred by a known method, that is, in an aqueous solution of about 110% ammonium nitrate at 60 for 6 hours, filtered, washed, and then washed at 500X. 5 hours This can be converted to a proton type and used.
  • the zeolite may be a zeolite exhibiting acidity exchanged with a metal ion in addition to the protonic zeolite.
  • a metal ion include monovalent metal ions such as Group IB metals such as Cu and Ag, and divalent or higher metal ions include Mg, Ca, and S Examples thereof include alkaline earth metals such as r and Ba, rare earth metals such as La and Ce, and transition metals such as Fe, Ni, Mn, Co, and V. These may be present at the same time as the protons in any proportion.
  • MFI zeolite those containing an element such as P which shows acidity can be used.
  • the content of P is preferably equal to or more than the content of protons and other metal thiones in terms of mole.
  • known methods are used. For example, a method of exchanging the cation of a metal atom with proton by ion exchange with a proton-type MFI zeolite, or a method of impregnating a salt-complex compound containing these elements into the MFI zeolite Is mentioned.
  • the above-mentioned MFI type zeolite catalyst is used as a third metal other than Si and A1 for the purpose of controlling activity, improving selectivity, suppressing coke formation and suppressing catalyst deterioration rate.
  • B, S n, G a, M n, F e and T i are converted to MFI zeolite Those contained in the skeleton of the structure can also be used.
  • the above MFI zeolite catalyst can be used after being subjected to steam treatment by a known method.
  • the temperature is preferably 5,000 to 750: the vapor pressure is preferably 0.1 to 1 MPa, and the processing time is preferably 10 to 48.
  • the above treatment can be performed after the catalyst is molded by the method described below.
  • the aforementioned catalyst is charged to the reactor in the following form. That is, MFI zeolite obtained by hydrothermal synthesis is essentially in a fine powder state.
  • the resulting finely powdered MFI zeolite catalyst may be directly charged into a fixed bed reactor, but in order to prevent pressure loss from increasing, a filler inert to the catalytic cracking, for example, silica pole However, it may be physically mixed with aluminum balls and filled. Further, the obtained fine powdered MFI zeolite catalyst may be kneaded with a sintering agent (binder) which does not change the catalytic performance, and then molded.
  • the sintering agent is typically a silica type, but may be selected from alumina, titania, zirconia, and diatomaceous types. ,
  • Sintering is preferably performed in the range of 500-800.
  • the shapes to be molded are: Tablets, Extrusion, Pellets, Spheres, Micro spheres, CDS Extrusion (CDS Extrusions)> Trilobes, Trilobes ), Quardlobes, Rings, Two-spoke rings (2 Sporkes rings;), HGS, EW, LDP and other special spokes, Ribs rings, Granules, etc. Can be exemplified.
  • catalytic cracking can be used in any type of reactor, such as a fixed bed, a fluidized bed, and a moving bed, but a fixed bed reactor with simple equipment can be used. preferable.
  • the catalytic cracking reaction is carried out by filling the above-mentioned catalyst into such a reactor and supplying the olefin-containing hydrocarbon raw material.
  • the reaction conditions are precisely controlled as follows.
  • the reaction temperature is 400 to 580, preferably 480 to 580 ° (:, more preferably 480 to 560. If the reaction temperature is lower than this range, supply On the other hand, if the reaction temperature is higher than this range, the rate of coke formation accelerates, and the catalyst conversion rate decreases. ⁇ The activity of the product decreases faster.
  • the reaction pressure is adjusted to 0.05 MPa to 2 MPa, preferably 0.05 to: L MPa, more preferably 0.05 to 0.5 MPa.
  • the feed rate (WHSV) of the entire raw material per unit weight of the MFI catalyst is 32 to 256 hr-1 or more, preferably 40 to 256 hr-1, more preferably 40 to: L28 hr-1. i. If the feed rate (WHSV) is lower than this range, the pentene content in the reaction distillate is reduced and the rate of catalyst activity reduction is suppressed to some extent, but hydrogen, saturated hydrocarbon and aromatic The yield of aromatic hydrocarbons increases and high selectivity and productivity of ethylene and propylene cannot be obtained. On the other hand, under the reaction conditions of the raw material supply rate (WHSV) larger than this range, the rate of coke formation is increased, which is not preferable.
  • the reactor may be a single reactor or a plurality of reactors.
  • the reaction conditions are more precisely controlled by installing the reactors in series. it can.
  • catalytic cracking operation is performed in one of the reactors, and regeneration and other operations are performed in the other reactor. It becomes. Under these reaction conditions, This maximizes the selectivity, yield and productivity of len, and suppresses the formation of coke, which causes a decrease in catalyst activity.
  • the weight ratio of pentene to propylene in the reaction product distillate at the reactor outlet is usually from 0.20 to 0.80, preferably from 0.25 to 0.8. It is preferably 80, more preferably 0.30 to 0.80.
  • the weight ratio of pentene to propylene in the reaction product distillate at the outlet of the first reactor is usually 0.20 to 0.80. It is preferably 0.25 to 0.80, more preferably 0.30 to 0.80.
  • the olefins having 4 or more carbon atoms, including pentene are separated from the distillate of the reaction product and then recycled to the catalytic cracking reactor to be combined with new raw materials. It is also possible to use these naphtha crackers together with new naphtha raw materials after separation of these carbons having 4 or more carbon atoms.
  • the raw material contains at least one kind of carbon having 4 to 12 carbon atoms, and contains 10 to 70 wt% of at least one kind of carbon having 1 to 12 saturated hydrocarbons.
  • the raw material containing 2 wt% or less of the gen compound in some cases
  • the feed rate (WH SV) of all raw materials per unit weight of the MFI catalyst is 32 to 256 hri, 400 to 5 at a reaction pressure of 0.05 to 2 MPa.
  • hydrogen and saturated hydrocarbons are controlled by controlling the weight ratio of pentene to propylene in the reaction product distillate to 0.20 to 0.80.
  • Example 1 In addition, it suppresses by-products such as aromatic hydrocarbons and coke, and also suppresses the deposition of coke on the catalyst, even in raw materials containing relatively large amounts of gen compounds, resulting in high propylene selectivity and long catalyst life. can get.
  • the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
  • Anmoniumu salt Z SM- 5 (S i 0 2 ZA l 2 0 3 molar ratio of 2 8 0) powder in 5 5 0 ° C, was calcined for 5 hours. After firing, a catalyst having a particle size of 250 to 500 m was obtained by compression molding, pulverization and classification.
  • the reaction was carried out in a fixed-bed flow reactor (10.7 mm ID, 250 mm length).
  • a quartz tube was filled with 0.125 g of the above catalyst and quartz wool and quartz sand as a holding material so that the entire length became 250 mm.
  • This quartz tube was charged into the reactor, the temperature of the catalyst layer was maintained at 550, and the C4 fraction raw material C (Table 1) obtained by cracking of naphtha was supplied at a flow rate of 8 g / hour.
  • the catalytic cracking reaction was performed under a reaction pressure of 0.5 MPa.
  • the effluent reaction product was kept in a gaseous state and analyzed using a gas chromatograph.
  • Table 2 shows the results of the reaction. This is a result that the productivity of ethylene and propylene can be stably obtained over 90 hours. In addition, the production yield of coke is low, and a method of burning and removing accumulated coke is used, so the amount of heat generated by coke combustion is small and the amount of steam generated that is not desirable for catalyst deterioration Less. Therefore, when the catalyst is used repeatedly, its life can be expected to be longer. Comparative Example 1
  • Example 1 A catalytic cracking reaction was carried out under the same conditions as in Example 1 except that the raw material C in Example 1 was changed to an n-butene raw material. Table 3 shows the results. Under these conditions, which use a raw material that does not contain the saturated hydrocarbon butane, the reaction time for stable production of ethylene and propylene was only 20 hours. Table 1 (Raw material composition)
  • Example 2 the same conditions as in Example 1 were used except that the raw materials shown in Table 4 were used, respectively, to obtain saturated hydrocarbons mainly of butanes at 18.4 wt%, 30.6 wt% and This is an example of catalytic cracking of a raw material containing 61.2 wt%.
  • Table 4 Compared to Comparative Example 1, the raw material contains only 18.4 wt% of saturated hydrocarbons, the coke production yield is reduced by half, and the reaction time for stable production of ethylene and propylene is 20 hours. It can be seen that the time has rapidly increased from 42 hours to 42 hours.
  • Example 4 is an example of catalytic cracking of a raw material having a saturated hydrocarbon content as high as 61.2 wt%. The operation was stopped at 100 hours, at which point the catalyst activity was slightly reduced. Table 4 (Examples 1 to 4, Comparative Example 1)
  • Example 5 catalytic cracking was carried out under the same reaction conditions as in Example 1 except that the reaction temperature was 500 ° C, the WHSV shown in Table 5 was used, and raw material D was used. . Table 5 shows the results. As shown in Example 5, the value of 1 2 8 hr 1 and higher conditions of feed rate of raw material (WHSV) of catalyst per weight unit, the weight ratio flop propylene pentenes to zero. 5 or more since it I have. Under these conditions, it can be seen that the formation of coke is extremely low.
  • Example 9 shows an example of repeated use of the catalyst.
  • the catalytic cracking reaction was performed, and the produced coke was burned.
  • the catalyst was held in the reactor, the raw materials were supplied under the same conditions as in Example 1, and the catalytic cracking reaction was restarted. After the reaction, coke combustion was performed under the same conditions. As a result of repeating this operation six times, no deterioration of the catalyst was observed.
  • Example 9, 10
  • Example 9 the same reaction conditions as in Example 1 were used except that butadiene was added to raw material C, and raw materials having butadiene contents of 0.51 and 1.1 wt% were used, respectively. Catalytic cracking was carried out. The results are shown in Figure 1. Compared with the butadiene content of Example 1 of 0.05 wt%, the propylene yield could be stably obtained for 60 hours or more even with the butadiene content of 1 lwt%. In addition, the production yield of coke was 37 ppm and 40 ppm, which was a slight increase.

Landscapes

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

Abstract

L'invention concerne un procédé pour produire une oléfine inférieure dont les composants principaux sont l'éthylène et le propylène. Selon ce procédé, une matière première d'hydrocarbure contenant des oléfines est soumise à un craquage catalytique au moyen d'un catalyseur à base de zéolite pour produire une oléfine inférieure à celles de la matière première. Une matière première contenant au moins une oléfine dotée de 4 à 12 atomes de carbone et 10 à 70 % en poids d'au moins un hydrocarbure saturé pourvu de 1 à 12 atomes de carbone sont mis en contact avec un catalyseur comprenant un catalyseur à base de zéolite MFI, sous une pression de réaction de 0,05 à 2 MPa, le débit de la matière première par unité de poids du catalyseur (WHSV) étant de 32 à 256 hr-1, à une température de réaction de 400 à 580 °C, pour produire de l'éthylène et du propylène. Cette invention permet de supprimer la formation de sous-produits tels que l'hydrogène, un hydrocarbure saturé, un hydrocarbure aromatique et du coke, de réduire la détérioration du catalyseur pour une durée prolongée, et de produire de manière ciblée et à haut rendement de l'éthylène et du propylène, même si la matière première utilisée contient une quantité relativement importante de diène qui diminue généralement l'activité du catalyseur.
PCT/JP2004/000676 2003-02-14 2004-01-27 Procede de production d'olefine inferieure WO2004072002A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2004544182A JP4335144B2 (ja) 2003-02-14 2004-01-27 低級オレフィンの製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2003-37318 2003-02-14
JP2003037318 2003-02-14
JP2003-150857 2003-05-28
JP2003150857 2003-05-28

Publications (1)

Publication Number Publication Date
WO2004072002A1 true WO2004072002A1 (fr) 2004-08-26

Family

ID=32871195

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/000676 WO2004072002A1 (fr) 2003-02-14 2004-01-27 Procede de production d'olefine inferieure

Country Status (4)

Country Link
JP (1) JP4335144B2 (fr)
KR (1) KR100714257B1 (fr)
TW (1) TWI243201B (fr)
WO (1) WO2004072002A1 (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006028333A1 (fr) * 2004-09-10 2006-03-16 Sk Corporation Catalyseur solide acide permettant de produire des olefines legeres et son procede d'utilisation
WO2007019787A1 (fr) * 2005-08-15 2007-02-22 China Petroleum & Chemical Corporation Procede de fabrication d’olefines inferieures sous pression negative
WO2007032447A1 (fr) * 2005-09-16 2007-03-22 Asahi Kasei Chemicals Corporation Procede pour produire de l'ethylene et du propylene
JP2007106739A (ja) * 2005-09-16 2007-04-26 Asahi Kasei Chemicals Corp エチレン及びプロピレンを製造する方法
JP2008050359A (ja) * 2006-08-24 2008-03-06 Ifp 球状ボールの形状を呈するマクロ細孔質触媒の存在下でのプロピレン生成方法
JP2010533743A (ja) * 2007-07-19 2010-10-28 中国石油化工股▲ふん▼有限公司 オレフィンの製造方法
JP2011020045A (ja) * 2009-07-15 2011-02-03 Mitsui Chemicals Inc 変性ゼオライト触媒および該変性ゼオライト触媒を用いた不飽和炭化水素類の製造方法
US7893311B2 (en) 2005-09-16 2011-02-22 Asahi Kasei Chemicals Corporation Method for producing ethylene and propylene
US8137631B2 (en) 2008-12-11 2012-03-20 Uop Llc Unit, system and process for catalytic cracking
US8246914B2 (en) 2008-12-22 2012-08-21 Uop Llc Fluid catalytic cracking system
US8299104B2 (en) 2004-01-25 2012-10-30 Sanofi-Aventis Deutschland Gmbh Aryl-substituted heterocycles, process for their preparation and their use as medicaments
US8889076B2 (en) 2008-12-29 2014-11-18 Uop Llc Fluid catalytic cracking system and process
JP5700376B2 (ja) * 2009-07-30 2015-04-15 三菱化学株式会社 プロピレンの製造方法及びプロピレン製造用触媒
WO2016017793A1 (fr) * 2014-08-01 2016-02-04 千代田化工建設株式会社 Procédé de préparation de propylène et catalyseur de préparation de propylène

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101298871B1 (ko) * 2011-02-24 2013-08-21 롯데케미칼 주식회사 에틸렌 및 프로필렌 제조방법
US9656928B2 (en) 2014-11-12 2017-05-23 King Fahd University Of Petroleum And Minerals Processes and catalysts for production of light olefins

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001034727A1 (fr) * 1999-11-10 2001-05-17 Exxon Research And Engineering Company Procede relatif a la production selective d'olefines legeres
WO2001090279A2 (fr) * 2000-05-19 2001-11-29 Exxonmobil Chemical Patents Inc. Utilisation d'un procede de production selective d'olefines c3 dans un procede de craquage catalytique sur lit fluidise

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001034727A1 (fr) * 1999-11-10 2001-05-17 Exxon Research And Engineering Company Procede relatif a la production selective d'olefines legeres
WO2001090279A2 (fr) * 2000-05-19 2001-11-29 Exxonmobil Chemical Patents Inc. Utilisation d'un procede de production selective d'olefines c3 dans un procede de craquage catalytique sur lit fluidise

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8299104B2 (en) 2004-01-25 2012-10-30 Sanofi-Aventis Deutschland Gmbh Aryl-substituted heterocycles, process for their preparation and their use as medicaments
WO2006028333A1 (fr) * 2004-09-10 2006-03-16 Sk Corporation Catalyseur solide acide permettant de produire des olefines legeres et son procede d'utilisation
JP2009505983A (ja) * 2005-08-15 2009-02-12 チャイナ ペトロリウム アンド ケミカル コーポレイション 陰圧下での低級オレフィン製造法
WO2007019787A1 (fr) * 2005-08-15 2007-02-22 China Petroleum & Chemical Corporation Procede de fabrication d’olefines inferieures sous pression negative
US7875756B2 (en) 2005-08-15 2011-01-25 China Petroleum & Chemical Corporation Process for producing lower olefins under negative pressure
US7893311B2 (en) 2005-09-16 2011-02-22 Asahi Kasei Chemicals Corporation Method for producing ethylene and propylene
WO2007032447A1 (fr) * 2005-09-16 2007-03-22 Asahi Kasei Chemicals Corporation Procede pour produire de l'ethylene et du propylene
US7884257B2 (en) 2005-09-16 2011-02-08 Asahi Kasei Chemicals Corporation Method for producing ethylene and propylene
JP2007106739A (ja) * 2005-09-16 2007-04-26 Asahi Kasei Chemicals Corp エチレン及びプロピレンを製造する方法
JP5014138B2 (ja) * 2005-09-16 2012-08-29 旭化成ケミカルズ株式会社 エチレン及びプロピレンを製造する方法
JP2008050359A (ja) * 2006-08-24 2008-03-06 Ifp 球状ボールの形状を呈するマクロ細孔質触媒の存在下でのプロピレン生成方法
US9024100B2 (en) 2007-07-19 2015-05-05 China Petroleum & Chemical Corporation Process for producing olefins
JP2010533743A (ja) * 2007-07-19 2010-10-28 中国石油化工股▲ふん▼有限公司 オレフィンの製造方法
US8137631B2 (en) 2008-12-11 2012-03-20 Uop Llc Unit, system and process for catalytic cracking
US8246914B2 (en) 2008-12-22 2012-08-21 Uop Llc Fluid catalytic cracking system
US8889076B2 (en) 2008-12-29 2014-11-18 Uop Llc Fluid catalytic cracking system and process
JP2011020045A (ja) * 2009-07-15 2011-02-03 Mitsui Chemicals Inc 変性ゼオライト触媒および該変性ゼオライト触媒を用いた不飽和炭化水素類の製造方法
JP5700376B2 (ja) * 2009-07-30 2015-04-15 三菱化学株式会社 プロピレンの製造方法及びプロピレン製造用触媒
WO2016017793A1 (fr) * 2014-08-01 2016-02-04 千代田化工建設株式会社 Procédé de préparation de propylène et catalyseur de préparation de propylène
JPWO2016017793A1 (ja) * 2014-08-01 2017-04-27 千代田化工建設株式会社 プロピレンの製造方法およびプロピレン製造用触媒

Also Published As

Publication number Publication date
JPWO2004072002A1 (ja) 2006-06-01
KR100714257B1 (ko) 2007-05-02
JP4335144B2 (ja) 2009-09-30
KR20050097513A (ko) 2005-10-07
TWI243201B (en) 2005-11-11
TW200424162A (en) 2004-11-16

Similar Documents

Publication Publication Date Title
US7754934B2 (en) Process for producing ethylene and propylene
KR920002241B1 (ko) 저급지방족 탄화수소의 제조방법
WO2004072002A1 (fr) Procede de production d'olefine inferieure
WO2007086839A1 (fr) Conversion sélective d'un composé oxygéné en propylène en utilisant une technologie de lit mobile et un système de catalyseur bifonctionnel stabilisé de façon hydrothermale
WO1996013331A1 (fr) Catalyseur de conversion d'hydrocarbure et procede de conversion catalytique avec ce catalyseur
US8034987B2 (en) Process for producing propylene and aromatic hydrocarbons, and producing apparatus therefor
US9994499B2 (en) Production of cyclic C5 compounds
CN112739802B (zh) 与裂化相结合的选择性氢解
US20070246400A1 (en) Zeolite Catalysts
JP6728351B2 (ja) 非環式ｃ５化合物の生成
TW201842969A (zh) 使觸媒恢復活力的方法
CA3004303C (fr) Procede de conversion de composes c5 acycliques en composes c5 cycliques et composition catalytique a utiliser dans celui-ci
EP3237581A1 (fr) Procédé de production d'hydrocarbures c2 et c3
US20230357654A1 (en) Process for converting naphtha to light olefins with separation
EP3371140B1 (fr) Procédé de conversion de composés c5 acycliques en composés c5 cycliques
WO2011143306A2 (fr) Procédé de conversion d'alcanes inférieurs en hydrocarbures aromatiques
US11135574B2 (en) Catalyst system and process for conversion of a hydrocarbon feed utilizing the catalyst system
US7875756B2 (en) Process for producing lower olefins under negative pressure
WO2015152159A1 (fr) Procédé de production d'hydrocarbure insaturé
KR101021206B1 (ko) 이동상 기술 및 열수 안정화된 이중작용성 촉매계를 사용한 산소화물의 프로필렌으로의 선택적 전환 방법
US20230357107A1 (en) Process for catalytically converting naphtha to light olefins
US20230399274A1 (en) Process for catalytically converting naphtha to light olefins with predominant modes
KR20220160107A (ko) 프로필렌의 제조방법
WO2023097253A1 (fr) Procédé intégré de production d'éthylène et de propylène à partir d'hydrocarbures en c4 et/ou en c5
JP2006131676A (ja) 高オクタン価ガソリン基材の製造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2004544182

Country of ref document: JP

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1020057013680

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 20048042051

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 1020057013680

Country of ref document: KR

122 Ep: pct application non-entry in european phase