WO2007071177A1 - Methode de conversion catalytique destinee a augmenter le rendement d'olefines inferieures - Google Patents

Methode de conversion catalytique destinee a augmenter le rendement d'olefines inferieures Download PDF

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Publication number
WO2007071177A1
WO2007071177A1 PCT/CN2006/003481 CN2006003481W WO2007071177A1 WO 2007071177 A1 WO2007071177 A1 WO 2007071177A1 CN 2006003481 W CN2006003481 W CN 2006003481W WO 2007071177 A1 WO2007071177 A1 WO 2007071177A1
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Prior art keywords
reaction
inhibitor
catalyst
oil
weight
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PCT/CN2006/003481
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English (en)
French (fr)
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WO2007071177A8 (fr
Inventor
Zheng Li
Jun Long
Shuandi Hou
Zhijian Da
Chaogang Xie
Jiushun Zhang
Zhanzhu Zhang
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China Petroleum & Chemical Corporation
Research Institute Of Petroleum Processing, Sinopec
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Application filed by China Petroleum & Chemical Corporation, Research Institute Of Petroleum Processing, Sinopec filed Critical China Petroleum & Chemical Corporation
Priority to JP2008546078A priority Critical patent/JP5692962B2/ja
Priority to KR1020087015917A priority patent/KR101397998B1/ko
Priority to US12/158,145 priority patent/US8608944B2/en
Publication of WO2007071177A1 publication Critical patent/WO2007071177A1/zh
Publication of WO2007071177A8 publication Critical patent/WO2007071177A8/zh

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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • 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
    • 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
    • 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a process for catalytic conversion of a hydrocarbon oil, and more particularly to a process for catalytically converting a hydrocarbon oil to a low-carbon olefin such as ethylene or propylene under the action of a catalyst.
  • the conventional method for producing low-carbon olefins from petroleum hydrocarbons is a steam cracking process, the reaction mechanism of which is a free radical thermal cracking mechanism of petroleum hydrocarbons, so that the ethylene yield of the process is high.
  • the mass ratio of propylene to ethylene prepared by steam cracking of naphtha is about 0.43, while the market requires that the mass ratio of propylene to ethylene is above 0.70, although the proper reduction of the reaction depth can increase the yield of propylene, but the quality of propylene and acetamidine.
  • the ratio should not exceed 0.65, otherwise it will lead to a decrease in the total olefin yield, which in turn affects the economics of the operation of the device.
  • the steam cracking method is suitable for light petroleum hydrocarbons such as ethane, propane, butane, natural gas, naphtha or light diesel oil.
  • light petroleum hydrocarbons such as ethane, propane, butane, natural gas, naphtha or light diesel oil.
  • the supply of light petroleum hydrocarbons is limited, forcing researchers have had to turn their attention to the use of a wider range of feedstocks, including heavy petroleum hydrocarbons, to make low-carbon olefins.
  • a catalytic cracking process for the preparation of propylene and butene is disclosed in U.S. Patent 4,980,053.
  • the method adopts a fluidized bed or a moving bed reactor and a solid acid catalyst, and the reaction temperature is 500-650 ° C, and the weight ratio of the catalyst to the feedstock is 2-12 when the feed weight space velocity is 0.2-20 Carry out the reaction.
  • Example 1 using ZSM-5 as the active component, kaolin as the carrier catalyst, using vacuum gas oil as the raw material, and when the reaction was carried out at 580 ° C, the ethylene yield was 5.89 wt%, and the yield of propionate was 21.56% by weight, butene yield was 15.64 weight 0 / 0 .
  • No. 6,210,562 discloses a process for the catalytic thermal cracking of ethylene and propylene.
  • the method enables preheating of heavy petroleum hydrocarbons in a riser or downcomer line reactor at elevated temperatures In the presence of steam, it is contacted with a column-containing clay zeolite and/or a catalyst of phosphorus and aluminum or magnesium or calcium-modified five-membered ring high silica zeolite at a reaction temperature of 650 to 750 ° C; and a reaction pressure of 1.5 to 4 ⁇ 0 ⁇ 10 5 Pa, the reaction time is 0.2 ⁇ 5 seconds, the weight ratio of catalyst to feed oil is 15 to 40: 1, 0.3 ⁇ 1 weight ratio of steam to feedstock oil: catalytic thermal cracking reaction under conditions 1.
  • the yield of both women and propylene of the method exceeded 18% by weight.
  • No. 6,106,697 discloses a process for the selective production of C2 to C4 olefins by catalytic cracking using a two-stage reactor using wax oil or residual oil as a raw material.
  • the wax oil or residue raw material is subjected to catalytic cracking reaction in contact with the large pore zeolite catalyst under normal catalytic cracking conditions to form different boiling range products including a gasoline fraction in a first-stage reactor;
  • the fraction enters the second stage reactor at a reaction temperature of 500 to 650.
  • the ratio of the agent to the oil is 4 to 10: 1.
  • the hydrocarbon partial pressure is 70 to 280 kPa, and the reaction is carried out by further contacting with the medium pore zeolite catalyst to form a C2 to C4 olefin.
  • the prior art methods for increasing ethylene, propylene, and butene are mainly higher reaction temperatures, ratios of fuel to oil, and steam injection than conventional catalytic cracking, and medium-sized pores having an average pore diameter of less than 0.7 nm.
  • the catalyst of the pore-selective zeolite, the above means will strengthen the cracking reaction of petroleum hydrocarbons, that is, the prior art aims to increase the production of ethylene, propylene and butene by strengthening the formation reaction of ethylene, propylene and butene.
  • the object of the present invention is to provide a catalytic conversion method for increasing the production of low-carbon olefins based on the discovery of the inventors, which will suppress the re-conversion reaction of low-carbon olefins such as propylene by using an inhibitor, thereby increasing the low The yield of carbon olefins, especially propylene.
  • the method provided by the invention comprises: contacting and reacting a hydrocarbon oil feedstock with a catalytic conversion catalyst in a catalytic conversion reactor comprising one or more reaction stages, wherein the hydrocarbon oil feedstock is catalytically converted in the presence of an inhibitor during the reaction Reaction, with or without inhibitor
  • the reaction oil and gas are separated from the catalyst after the reaction, wherein the reaction oil and gas are separated to obtain the desired product containing ethylene and propylene, and the carbon deposition catalyst is stripped and regenerated and returned to the reaction section for recycling.
  • the hydrocarbon oil feedstock of the present invention is selected from the group consisting of one or more of petroleum hydrocarbon oil, mineral oil and synthetic oil, wherein the petroleum hydrocarbon oil is selected from the group consisting of C4 to C6 fractions, gasoline, diesel oil, vacuum gas oil, a mixture of one or more of coker gas oil, deasphalted oil, hydrogenated tail oil, atmospheric residue, vacuum residue, and crude oil; mineral oil selected from the group consisting of coal liquefied oil, oil sand oil, and shale oil One or more mixtures; the synthetic oil is a distillate obtained by FT synthesis of coal, natural gas or pitch.
  • the catalytic conversion catalyst of the present invention comprises zeolite, inorganic oxide and optionally clay, and the content of each component is: zeolite 10 ⁇ 50% by weight, inorganic oxide 5 ⁇ 90% by weight, clay 0 ⁇ 70% by weight .
  • the zeolite is used as an active component, and is selected from medium pore zeolites having an average pore diameter of less than 0.7 nm and optionally a large pore zeolite having an average pore diameter of more than 0.7 nm.
  • the medium pore zeolite accounts for 25 to 100% by weight of the active component, preferably 50 to 100%.
  • the heavy %, large pore zeolite accounts for 0 to 75 wt% of the active component, preferably 0 to 50 wt%.
  • the medium pore zeolite is selected from the ZSM series zeolite and/or the ZRP zeolite, and the above-mentioned medium pore zeolite may be modified with a non-metal element such as phosphorus and/or a transition metal element such as iron, cobalt or nickel, and a more detailed description of the ZRP.
  • a non-metal element such as phosphorus and/or a transition metal element such as iron, cobalt or nickel
  • ZRP a more detailed description of the ZRP.
  • the macroporous zeolite is selected from the group consisting of rare earth Y (REY), rare earth hydrogen Y (REHY), ultra-stable Y obtained by different methods, and high-silicon cerium.
  • REY rare earth Y
  • REHY rare earth hydrogen Y
  • ultra-stable Y obtained by different methods
  • high-silicon cerium high-silicon cerium.
  • the inorganic oxide is used as a binder and is selected from the group consisting of silicon dioxide (SiO 2 ) and/or aluminum oxide (Al 2 2 3 3 ).
  • the clay acts as a substrate (i.e., a carrier) selected from the group consisting of kaolin and/or halloysite.
  • the reaction section of the catalytic conversion reactor of the present invention is selected from one or more risers, one or more fluidized beds, one or more downcomers, risers + fluidized beds, risers + down Tube, down tube + fluidized bed and a modified version based on them, wherein the riser may be an equal diameter riser or a variety of variable diameter risers.
  • the inhibitor according to the present invention is or includes a mixture of a substance having a hydrogen-donating ability, a substance having a reducing ability, and a substance capable of adsorbing on an active site of an acidic catalyst.
  • the substance having hydrogen supply capability is or comprises a mixture of one or more of hydrogen, tetrahydronaphthalene, decalin, catalytic cracking dry gas and coking dry gas; the substance having reducing ability is or contains carbon monoxide;
  • the substance adsorbed on the active site of the acidic catalyst is or contains one or a mixture of one or more of decyl alcohol, ethanol, ammonia, and pyridine.
  • the inhibitor injection site of the present invention comprises a hydrocarbon oil feedstock feed line, a regenerated catalyst transfer line, a reaction section of the reactor, a settler for separating the reaction oil and gas from the carbon deposition catalyst, and a catalyst for stripping the carbon deposition catalyst. Any part of the stripper.
  • the inhibitor When the inhibitor is injected from the reaction zone of the reactor, it is preferred that the inhibitor be injected downstream of the catalyst inlet of the reaction zone.
  • the inhibitor be injected between the plurality of reaction stages.
  • the inhibitor is injected between the riser and the fluidized bed, but The nature of the feedstock and catalyst are different and it is not excluded that the inhibitor is injected from other locations downstream of the catalyst inlet of the riser.
  • variable diameter riser When a variable diameter riser is employed, it is preferred that the inhibitor be injected from the variable diameter of the variable diameter riser, but due to the nature of the feedstock and catalyst, it is not excluded that the inhibitor is injected from other locations downstream of the catalyst inlet of the riser.
  • the weight ratio of the inhibitor to the hydrocarbon oil feedstock is from 0.001 to 15% by weight, preferably from 0.003 to 10% by weight, based on the weight of the hydrocarbon oil feedstock.
  • the inhibitor of the present invention may be injected at one point or at the same time, and the amount of injection per point is 0 to 100% by weight of the total amount of the inhibitor.
  • the inhibitor amount of the inhibitor of the present invention is an inhibitor separated from the reaction product.
  • reaction product and inhibitor separation process of the present invention is carried out in a product separation apparatus commonly used in the art.
  • the reaction temperature of the hydrocarbon oil feedstock is 500-700 ° C, preferably 550-650 ° C; used to make the reaction oil and gas and carbon deposition catalyst
  • the pressure of the separated settler is 1.5 ⁇ 4x10 5 Pa, preferably 1 ⁇ 5 ⁇ 3 ⁇ 5 ⁇ 10 5 Pa; the reaction time is 0.5-10 seconds, preferably 1 ⁇ 5 seconds; the weight ratio of catalyst to hydrocarbon oil raw material is 6 ⁇ 40 , preferably 10 to 30; the weight ratio of water vapor to hydrocarbon oil raw material is 0.1 to 1:1, preferably 0.2 to 0.6:1.
  • the present invention has the following advantages:
  • the present invention can be further lower olefins conversion reaction after the generation of weakening to the original levels of 50 to 70% passing inhibitor injection means, thereby increasing the yield of the desired product; when vacuum gas oil as raw material , ethylene yield as high as 8.7: 3 weight%, a propylene yield of up to 29.30 weight percent respectively, 14.4% and 26.6% than without inhibitor injection.
  • the present invention can reduce the amount of steam by injecting an inhibitor into the reactor, thereby alleviating the problem of hydrothermal deactivation of the catalyst to a certain extent and prolonging the service life of the catalyst.
  • the process of the present invention has a wide range of raw materials, including C4 C6 fractions, gasoline fractions, and various heavy hydrocarbons, and can be implemented with minor modifications to existing equipment, with a wide range of applications.
  • Fig. 1 is a schematic view showing the process of catalytic conversion of a low-carbon olefin provided by the present invention.
  • an inhibitor is injected from a raw material nozzle into a reaction section and recycled.
  • FIG. 2 is a schematic flow chart of a catalytic conversion process for increasing the production of light olefins provided by the present invention.
  • the inhibitor is injected from a stripper and used in a single pass. detailed description
  • the present invention can have various specific embodiments depending on the nature of the raw material and the catalyst, and the inhibitor is injected into the reaction section from the raw material nozzle in combination with FIG. 1 and FIG.
  • the method of the present invention is described in detail by recycling and injecting the inhibitor from the stripper and using it in a single pass, but the invention is not so limited.
  • Figure 1 is a schematic flow diagram of an inhibitor injected into a reaction zone from a feed nozzle and recycled.
  • the hot regenerated catalyst enters the bottom of the riser 4 via the regenerant transfer line 16 and accelerates upward flow under the action of the pre-lifting medium injected by line 1.
  • the preheated hydrocarbon oil feedstock is mixed with the atomized steam from line 3 and the inhibitor from line 14 in a certain ratio via line 2, and then injected into the riser 4 to contact and react with the hot catalyst in the presence of the inhibitor.
  • the outlet temperature of the riser 4 is 5 00 ⁇ 700X
  • the pressure of the settler 7 is 1.5 ⁇ 4x10 s
  • the reaction time is 0.5 ⁇ 10 seconds
  • the weight ratio of raw materials is 6 ⁇ 40.
  • the mixture of reaction oil and gas, inhibitor and catalyst proceeds along the riser to the riser outlet and enters the settler 7, where the reacted hydrocarbons with or without the inhibitor are separated from the carbonaceous catalyst.
  • the reaction oil and gas and the inhibitor are sent to the subsequent separation system 9 through the pipeline 8 to continue the separation.
  • the reaction product is taken out through the pipeline 10, and the reaction product is further separated to obtain the target product propylene, ethylene, etc., and gasoline, diesel oil, heavy oil, etc.
  • a part of the inhibitor is taken out via line 11, and another part of the inhibitor is passed through line 12 into separator 13 for further separation and refining, mixed with fresh inhibitor from line 14, and then passed through line 3 with atomizing steam into the reaction section. use.
  • the carbonaceous catalyst enters the stripper 6, and the stripping steam is injected through the pipeline 5, and is in countercurrent contact with the carbonaceous catalyst, and the reaction oil and gas carried by the carbonaceous catalyst is stripped as clean as possible.
  • the stripped catalyst is sent to the regenerator 18 via the green agent transfer line 15 for charring regeneration.
  • An oxygen-containing gas such as air is injected into the regenerator 18 via line 17, and the regenerated flue gas is withdrawn via line 19.
  • the regenerated catalyst is returned to the riser 4 for recycling via the regenerant transfer line 16.
  • FIG. 2 is a schematic illustration of the flow of an inhibitor injected from a stripper and used in a single pass.
  • the hot regenerated catalyst enters the bottom of the riser 4 via the regenerant transfer line 16 and accelerates upward flow under the action of the pre-lifting medium injected by line 1.
  • the preheated hydrocarbon oil feedstock is mixed with the atomized steam from the pipeline 3 in a certain ratio through the pipeline 2, and then injected into the riser 4 to contact and react with the hot catalyst, and the outlet temperature of the riser 4 is 500 to 700.
  • the pressure of the settler 7 is 1.5 ⁇ 4x10 5 Pa
  • the reaction time is 0.5-10 seconds
  • the weight ratio of the catalyst to the hydrocarbon oil raw material is 6-40.
  • the mixture of the reaction oil and the catalyst proceeds up the riser to the outlet of the riser and then enters the settler 7, where the reaction oil and gas are separated from the catalyst of the carbon deposit.
  • the reaction oil is sent to the subsequent separation system via line 8 to complete the product separation, and the carbon-deposited catalyst enters the stripper 6 after the reaction.
  • the stripping steam and the inhibitor from the line 14 are injected through the line 5, and the stripping steam is in countercurrent contact with the carbon-deposited catalyst, and the reaction oil and gas carried by the carbon-deposited catalyst is stripped as clean as possible; the inhibitor is subjected to the stripper 6 Entering the settler 7 inhibits further secondary conversion of ethylene and propylene, and then enters the product separation system along with the reaction oil and gas.
  • the stripped catalyst is sent to the regenerator 18 via the spent feed line 15 for charring regeneration.
  • An oxygen-containing gas such as air is injected into the regenerator 18 via line 17, and the regenerated flue gas is withdrawn via line 19.
  • the regenerated catalyst is returned to the riser 4 for recycling via the regenerant transfer line 16.
  • the method provided by the present invention is further illustrated by the following examples, but the present invention is not limited thereby.
  • the catalyst used in the examples was industrially produced by Qilu Branch of Catalyst of China Petroleum & Chemical Corporation, and the product grade was MMC- 2 .
  • the raw material A used in the examples was pure propylene gas having a propylene concentration of more than 99.9 % by volume, and the raw material B was a vacuum gas oil, the main properties of which are shown in Table 1.
  • This example illustrates the catalytic activity of a low carbon olefin in a small fixed fluidized bed reactor using the method provided by the present invention with carbon monoxide as an inhibitor.
  • the experiment uses the raw material A as the raw material, and adopts the batch operation mode.
  • the raw materials, the inhibitor and the atomized steam are heated to about 350 ° C in the preheating furnace, and then enter the bottom of the fluidized bed reactor through the feeding nozzle, and are catalyzed by contact with the hot catalyst. Conversion reaction.
  • the reaction product and the inhibitor are separated from the catalyst and then enter the product separation system, and the reaction product is further separated into a gas product and a liquid product.
  • the stripping stage is carried out, and the hydrocarbon product adsorbed on the catalyst to be produced is vaporized by steam.
  • an oxygen-containing gas is introduced into the reactor to regenerate the catalyst to be produced, and after the catalyst is regenerated, the next reaction can be carried out.
  • the main operating conditions and results of the experiment are listed in Table 2.
  • This example illustrates the catalytic activity of a low-carbon olefin in the absence of an inhibitor during the reaction to further illustrate the effect of the present invention.
  • This example is an experiment discovered by the inventors in the laboratory different from conventional knowledge. phenomenon.
  • the experiment used the raw material A as the raw material, the reactor used and the main experimental steps and other operating conditions were the same as those in the first embodiment, and the main operating conditions and results are shown in Table 2.
  • Example 2 Comparing the experimental results of Example 1 and Example 1 in Table 2, it can be seen that propylene has a relatively high reactivity under the reaction conditions of conventional catalytic conversion to olefins, and the conversion ratio of propylene conversion reaction is 55.19% by weight. This is quite different from the understanding of most researchers. While the method proposed by the present invention can greatly suppress the secondary conversion reaction of propylene, the conversion of propylene in Example 1 is decreased by 22.8 percentage points.
  • Example 2
  • This example illustrates the catalytic activity of a low carbon olefin in a small fixed fluidized bed reactor using the method provided by the present invention with hydrogen as an inhibitor.
  • the experiment used the raw material A as the raw material.
  • the reactor used and the main experimental procedures were the same as those in the first embodiment.
  • the main operating conditions and results are shown in Table 2.
  • This example illustrates the catalytic activity of a low-carbon olefin in the absence of an inhibitor during the reaction to further illustrate the effect of the present invention.
  • This example is an experiment discovered by the inventors in the laboratory different from conventional knowledge. phenomenon.
  • the experiment used the raw material A as the raw material, the reactor used and the main experimental steps and other operating conditions were the same as those in the second embodiment.
  • the main operating conditions and results are shown in Table 2.
  • Example 2 Comparing the experimental results of Example 2 and Example 2 in Table 2, it can be seen that propylene has a relatively high reactivity under the reaction conditions of conventional catalytic conversion to olefins, and the conversion rate of propylene conversion reaction is 64.01% by weight. This is quite different from the understanding of most researchers. However, the method proposed by the present invention can greatly suppress the secondary conversion reaction of propylene, and the conversion rate of propylene in Example 2 is decreased by 29.97 percentage points.
  • Example 3
  • This example illustrates the catalytic activity of a low olefinic hydrocarbon in a small fixed fluidized bed reactor using the method provided by the present invention with ammonia as an inhibitor.
  • This example illustrates the use of the method of the present invention to catalytically convert heavy hydrocarbons to ethylene and propylene when the inhibitor is injected at different locations.
  • raw material B was used as a raw material, and methanol was used as an inhibitor to carry out catalytic conversion experiments on a medium-sized riser device for continuous reaction-regeneration operation.
  • the riser has an inner diameter of 16 mm and a height of 6 m.
  • the inner diameter of the fluidized bed reaction section is 64 mm and the height is 0.3 m.
  • the experiment adopts a single-pass operation mode, and the injection position of the inhibitor is a raw material nozzle.
  • the regenerated catalyst with a temperature of about 700 °C enters the bottom of the riser reaction section through the regeneration inclined tube and flows upward under the action of pre-lifting steam.
  • the raw material oil is heated to 350 by preheating furnace After mixing at about °c with the atomized water vapor and the inhibitor, it is sequentially introduced into the riser reaction section and the fluidized bed reaction section through the feed nozzle, and is contacted with the hot catalyst to carry out a catalytic conversion reaction.
  • the reaction product, the inhibitor and the water vapor and the catalyst to be produced enter the settler from the outlet of the fluidized bed reaction section, and the reaction product and the inhibitor are rapidly separated from the catalyst in the settler, and the reaction product is further separated into a gas product and a liquid product, and
  • the catalyst to be produced enters the stripper by gravity, and the steam vapor strips the hydrocarbon product adsorbed on the catalyst to be introduced into the gas-solid separation system through the fluidized bed reaction section.
  • the stripped catalyst is introduced into the regenerator and brought into contact with the heated air for regeneration.
  • the regenerated catalyst is stripped with water vapor in the transfer line to remove non-hydrocarbon gas impurities adsorbed and carried by the regenerated catalyst.
  • the stripped regenerated catalyst is returned to the riser reaction section for recycling.
  • This comparative example illustrates the case where ethylene and propylene are catalytically converted from heavy hydrocarbons in the absence of an inhibitor during the reaction to further illustrate the effect of the present invention.
  • the main operating conditions and results are shown in Table 3.
  • the raw material B was equal in pressure at the inlet of the riser reaction section to ensure that the conversion of the raw material was not affected by the change in partial pressure.
  • Example 5 Comparing the experimental results of Example 4 and Comparative Example in Table 3, it can be seen that the method provided by the present invention can obtain higher ethylene, on the basis of the existing petroleum hydrocarbon catalytic conversion to produce low carbon olefin technology. The yield of propylene was 14.4% and 26.6% higher than that of the comparative examples without injecting inhibitors.
  • Example 5 Comparing the experimental results of Example 4 and Comparative Example in Table 3, it can be seen that the method provided by the present invention can obtain higher ethylene, on the basis of the existing petroleum hydrocarbon catalytic conversion to produce low carbon olefin technology. The yield of propylene was 14.4% and 26.6% higher than that of the comparative examples without injecting inhibitors.
  • Example 5 Comparing the experimental results of Example 4 and Comparative Example in Table 3, it can be seen that the method provided by the present invention can obtain higher ethylene, on the basis of the existing petroleum hydrocarbon catalytic conversion to produce low carbon olefin technology. The yield of propylene was 14.4% and 26.6% higher than that of the comparativ
  • This example illustrates the use of the method of the present invention to catalytically convert heavy hydrocarbons to ethylene and propylene when the inhibitor is injected at different locations.
  • This example illustrates the use of the method of the present invention to catalytically convert heavy hydrocarbons to ethylene and propylene when the inhibitor is injected at different locations.
  • the experiment uses raw material B as the raw material and decahydronaphthalene as the inhibitor.
  • the injection position of the inhibitor is the pre-lifting steam distributor.
  • the reaction apparatus and main experimental procedures used in the experiment were the same as in Example 4, and the main operating conditions and results are shown in Table 3.
  • the yields of ethylene and propylene were as high as 8.15% by weight and 27.88% by weight, respectively.
  • Example 7
  • This embodiment illustrates the use of the method provided by the present invention to catalyze the conversion of heavy hydrocarbons to ethylene and propylene when the device produces self-produced dry gas as a suppressant and the inhibitor is recycled and injected at the raw material nozzle.
  • the raw material B was used as the raw material, and the reaction apparatus and main experimental procedures used in the experiment were the same as those in the fourth embodiment.
  • the main operating conditions and results are shown in Table 3.
  • the yields of ethylene and propylene were as high as 8.29 wt% and 28.52 wt%, respectively.
  • weight percent conversion weight of propylene in the amount of propylene (g) -: amount of propylene feed (g) table 3

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一种增产低碳烯烃的催化转化方法 技术领域
本发明属于烃油的催化转化方法， 更具体地说， 是一种烃油在催 化剂的作用下催化转化制取乙烯、 丙烯等低碳烯烃的方法。 背景技术
从石油烃制取低碳烯烃的传统方法是蒸汽裂解法， 其反应机理为 石油烃的自由基热裂解机理， 因此该方法的乙烯产率较高。 一般用石 脑油蒸汽裂解制取的丙烯与乙烯的质量比大约为 0.43, 而市场则要求 丙烯与乙烯的质量比达到 0.70以上， 尽管适当降低反应深度可以增产 丙烯， 但是丙烯与乙浠的质量比也不宜超过 0.65, 否则就会导致总烯 烃收率下降， 进而影响装置运行的经济性。 另外， 蒸汽裂解法适用的 原料为乙烷、 丙烷、 丁烷、 天燃气、 石脑油或轻柴油等轻质石油烃， 随着原油日趋变重， 轻质石油烃的供应量受到限制， 迫使研究者不得 不将注意力转移到使用包括重质石油烃在内的更宽范围的原料来制取 低碳烯烃。
近年来， 一些专利文献公开了使用重质石油烃、石脑油和 C4 ~ C6 轻烃等原料在酸性沸石上通过催化裂化反应制取低碳烯烃的方法。 与 蒸汽裂解相比， 该类方法具有两个优势： 一是石油烃在酸性沸石催化 剂上的反应遵循正碳离子机理， 因此气体反应产物中可以获得较高的 丙烯与乙烯的质量比； 二是利用成熟的流化催化裂化工程技术， 该类 方法既可以处理轻质石油烃原料， 也可以处理重质石油烃原料。
US4,980,053 中公开了一种制取丙烯和丁烯的催化裂解方法。 该 方法采用流化床或移动床反应器和固体酸性催化剂， 在反应温度为 500-650 °C , 进料重量空速为 0.2〜20时 催化剂与原料油的重量比为 2-12的条件下进行反应。 实施例 1使用 ZSM-5为活性组分、 高岭土 为载体的催化剂， 以减压瓦斯油为原料， 并在 580 °C下进行反应时， 其乙烯产率为 5.89重％, 丙浠产率为 21.56重％, 丁烯产率为 15.64 重0 /0。
US6,210,562 公开了一种催化热裂解制取乙烯和丙烯的方法。 该 方法使预热的重质石油烃在提升管或下行式输送线反应器内， 在高温 蒸汽存在下与含层柱粘土沸石和 /或经磷和铝或镁或钙改性的五元环高 硅沸石的催化剂接触， 在反应温度为 650 ~750 °C；、 反应压力为 1.5〜4·0χ105帕、 反应时间为 0.2〜5 秒、 催化剂与原料油的重量比为 15-40： 1、 水蒸汽与原料油的重量比为 0.3〜1： 1的条件下进行催化热 裂解反应。 该方法的乙婦和丙烯产率均超过 18重％。
US6,106,697公开了一种以蜡油或渣油为原料、 采用两级反应器 进行催化裂化反应选择性生产 C2〜C4 烯烃的方法。 蜡油或渣油原料 在第一级反应器中， 在常规催化裂化条件下与大孔沸石催化剂接触进 行催化裂化反应生成包括汽油馏分在内的不同沸程产物； 笫一级反应 器生成的汽油馏分进入第二级反应器中， 在反应温度 500~650。 ( 、 剂 油比为 4〜10： 1、 烃分压为 70〜280千帕条件下与中孔沸石催化剂接触 进行进一步反应生成 C2〜C4烯烃。
综上所述， 现有技术中增产乙烯、 丙烯、 丁烯的手段主要为采用 比常规.催化裂化更高的反应温度、 剂油比和蒸汽注入量， 以及采用含 有平均孔径小于 0.7 纳米的中孔择形沸石的催化剂， 上述手段都会强 化石油烃类的裂化反应， 即现有技术都是通过强化乙烯、 丙烯、 丁烯 的生成反应来达到增产乙烯、 丙烯、 丁烯的目的。 一直以来， 本领域 普通技术人员通常认为丙烯是催化裂化反应条件下的稳定反应产物； 《催化裂化工艺与工程（笫二版）》（陈俊武， 中国石化出版社， 2005 年 3月 1 日出版） 一书中正文第 152 页曾有这样的描述： "丙烯属稳 定产物， 在高转化率时基本不再转化"。 然而， 发明人通过实验室研 究意外地发现： 在石油烃催化转化制取低碳烯烃的反应条件及酸性沸 石存在下， 丙烯具有显著的反应活性， 它可以大量、 快速地转化成为 其它烃类、 氢气和焦炭， 导致丙烯收率反而会有所下降。 发明内容
本发明的目的正是在发明人发现的基础上提出一种增产低碳烯烃 的催化转化方法， 该方法将通过使用抑制剂来抑制已生成的丙烯等低 碳烯烃的再转化反应， 从而提高低碳烯烃特别是丙烯的收率。
本发明提供的方法包括： 烃油原料与催化转化催化剂在包括一个 或多个反应段的催化转化反应器内接触并反应， 在反应过程中使烃油 原料在抑制剂存在的情况下发生催化转化反应， 将含或不含抑制剂的 反应油气与反应后积炭的催化剂分离， 其中反应油气经分离得到含有 乙烯、 丙烯的目的产物， 积炭的催化剂经汽提、 再生后返回反应段循 环使用。
本发明所述的烃油原料选自石油烃油、 矿物油和合成油中的一种 或一种以上的混合物， 其中石油烃油选自 C4〜C6馏分、 汽油、 柴油、 减压瓦斯油、 焦化瓦斯油、 脱沥青油、 加氢尾油、 常压渣油、 减压渣 油和原油中的一种或一种以上的混合物； 矿物油选自煤液化油、 油砂 油和页岩油中的一种或一种以上的混合物； 合成油为煤、 天然气或沥 青经过 F-T合成得到的馏分油。
本发明所述的催化转化催化剂包括沸石、 无机氧化物和任选的粘 土， 各组分的含量分别为： 沸石 10 ~ 50 重％、 无机氧化物 5 ~ 90 重 %、 粘土 0 ~ 70重％。
其中沸石作为活性组分， 选自平均孔径小于 0.7 纳米的中孔沸石 和任选的平均孔径大于 0.7 纳米的大孔沸石， 中孔沸石占活性组分的 25 ~ 100重％, 优选 50 ~ 100重％, 大孔沸石占活性组分的 0 ~ 75重 %, 优选 0 ~ 50重％。 中孔沸石选自 ZSM系列沸石和 /或 ZRP沸石， 也可对上述中孔沸石用磷等非金属元素和 /或铁、 钴、 镍等过渡金属元 素进行改性， 有关 ZRP 更为详尽的描述参见 US5,232,675, ZSM 系 列沸石选自 ZSM-5、 ZSM-8, ZSM-11、 ZSM-12、 ZSM-23、 ZSM-35, ZSM-38, ZSM-48和其它类似结构的沸石之中的一种或一种以上的混 合物， 有关 ZSM-5更为烊尽的描述参见 US3，702，886。 大孔沸石选自 由稀土 Y ( REY )、 稀土氢 Y ( REHY )、 不同方法得到的超稳 Y、 高 硅 Υ构成的这组沸石中的一种或一种以上的混合物。 上述沸石都是可 以在市场上购买到的商业化产品。
无机氧化物作为粘接剂， 选自二氧化硅（Si02 ) 和 /或三氧化二铝 ( A1203 )。
粘土作为基质 （即载体）， 选自高岭土和 /或多水高岭土。
本发明所述的催化转化反应器的反应段选自一个或一个以上的提 升管、 一个或一个以上的流化床、 一个或一个以上的下行管、 提升管 +流化床、 提升管 +下行管、 下行管 +流化床以及在它们基础上改进 的型式， 其中提升管可以是等直径的提升管也可以是各种变直径的提 升管。 本发明所述的抑制剂是或包含具备供氢能力的物质、 具备还原能 力的物质和能够吸附在酸性催化剂活性中心上的物质中的一种或一种 以上的混合物。 其中具备供氢能力的物质是或包含氢气、 四氢萘、 十 氢萘、 催化裂化干气和焦化干气中的一种或一种以上的混合物； 具备 还原能力的物质是或包含一氧化碳； 能够吸附在酸性催化剂活性中心 上的物质是或包含曱醇、 乙醇、 氨、 吡啶中的一种或一种以上的混合 物。
本发明所述的抑制剂注入位置包含烃油原料进料管线、 再生催化 剂输送管线、 反应器的反应段、 用于使反应油气与积炭催化剂分离的 沉降器和用于汽提积炭催化剂的汽提器中的任一部分。
当抑制剂从反应器的反应段注入时， 优选抑制剂从反应段的催化 剂入口的下游注入。
当采用具有多个反应段的反应器时， 优选抑制剂在多个反应段之 间注入， 如采用提升管 +流化床时， 优选抑制剂在提升管与流化床之 间注入， 但由于原料和催化剂的性质不同， 不排除抑制剂从提升管的 催化剂入口的下游其它位置注入。
当采用变直径的提升管时， 优选抑制剂从变直径的提升管的变直 径处注入， 但由于原料和催化剂的性质不同， 不排除抑制剂从提升管 的催化剂入口的下游其它位置注入。
以烃油原料的重量为计算基准， 所述的抑制剂与烃油原料的重量 比为 0.001〜15重％， 优选 0.003~10重％。
本发明所述的抑制剂可以由一点注入， 也可以由一点以上同时注 入， 每点的注入量为抑制剂总注入量的 0~100重％。
本发明所述的抑制剂循环量为从反应产物中分离出的抑制剂的
0〜； 100重％, 即可以不循环， 也可以部分或完全循环使用。
本发明所述的反应产物和抑制剂分离过程在本领域常用的产物分 离设备内完成。
在本发明所述方法中， 烃油原料的反应温度， 特指反应器最后一 个反应段的出口温度， 为 500~700 °C， 优选 550〜650 °C ; 用于使反应 油气与积炭催化剂分离的沉降器的压力为 1.5〜4xl05 帕， 优选 1·5〜3·5χ105帕； 反应时间为 0.5~10 秒， 优选 1〜5秒； 催化剂与烃油 原料的重量比为 6〜40 , 优选 10〜30； 水蒸汽与烃油原料的重量比为 0.1〜1： 1, 优选 0.2〜0.6： 1。
与现有技术相比， 本发明具有以下优点：
1、 本发明通过注入抑制剂的手段可以将低碳烯烃在生成之后的 再转化反应削弱至原有水平的 50~70%， 从而提高目的产物产率； 当 以减压瓦斯油为原料时， 乙烯产率高达 8.7：3重％， 丙烯产率高达 29.30 重％， 分别比不注入抑制剂时提高了 14.4%和 26.6%。
2、 本发明通过向反应器内注入抑制剂可以减少蒸汽的用量， 进 而在一定程度上緩解催化剂的水热失活问题， 延长催化剂的使用寿 命。
3、 本发明所述的方法原料来源广泛， 包括 C4 C6馏分、 汽油馏 分以及各种重质烃类， 而且对现有的装置稍作改动即可实施， 应用范 围较宽。 附图说明
图 1是本发明提供的增产低碳烯烃的催化转化方法流程示意图， 在该图中， 抑制剂从原料喷嘴注入反应段并循环使用。
图 2是本发明提供的增产低碳烯烃的催化转化方法流程示意图， 在该图中， 抑制剂从汽提器注入并单程使用。 具体实施方式
由于本发明所述的抑制剂可以由不同位置注入， 因而本发明可以 根据原料和催化剂的性质不同有多种具体实施方式， 下面结合图 1和 图 2分别以抑制剂从原料喷嘴注入反应段并循环使用和抑制剂从汽提 器注入并单程使用为例详细说明本发明提供的方法， 但本发明并不因 此受到任何限制。
图 1 是抑制剂从原料喷嘴注入反应段并循环使用时的流程示意 图。 在该图所示的方法中， 热的再生催化剂经再生剂输送管线 16 进 入提升管 4的底部， 并在由管线 1注入的预提升介质的作用下加速向 上流动。 预热后的烃油原料经管线 2与来自管线 3的雾化蒸汽和来自 管线 14的抑制剂按一定比例混合后， 注入提升管 4, 在抑制剂存在的 情况下与热催化剂接触、 反应， 提升管 4 的出口温度为 500~700X , 沉降器 7压力为 1.5〜4xlOs帕， 反应时间为 0.5〜10秒， 催化剂与烃油 原料的重量比为 6~40。 反应油气、 抑制剂和催化剂的混合物沿提升管 上行至提升管出口处后进入沉降器 7, 在沉降器 7 内含或不含抑制剂 的反应油气与积炭的催化剂分离。 反应油气和抑制剂经管线 8送入后 续分离系统 9继续分离， 分离后反应产物经管线 10 引出， 反应产物 进一步分离得到目的产物丙烯、 乙烯等和汽油、 柴油、 重油等 （图中 未标出）， 一部分抑制剂经管线 11引出， 另一部分抑制剂则经管线 12 进入分离器 13进行进一步分离精制后， 与来自管线 14的新鲜抑制剂 混合后经管线 3与雾化蒸汽一起进入反应段循环使用。 而反应后积炭 的催化剂进入汽提器 6， 汽提蒸汽经管线 5 注入， 与积炭的催化剂逆 流接触， 将积炭的催化剂所携带的反应油气尽可能地汽提干净。 汽提 后的催化剂经待生剂输送管线 15送入再生器 18烧焦再生。 含氧气体 如空气经管线 17注入再生器 18, 再生烟气经管线 19引出。 再生后的 催化剂经再生剂输送管线 16返回提升管 4循环使用。
图 2是抑制剂从汽提器注入并单程使用的流程示意图。 在该图所 示的方法中， 热的再生催化剂经再生剂输送管线 16进入提升管 4 的 底部， 并在由管线 1 注入的预提升介质的作用下加速向上流动。 预热 后的烃油原料经管线 2与来自管线 3的雾化蒸汽按一定比例混合后， 注入提升管 4与热催化剂接触、反应，提升管 4的出口温度为 500~700 。C， 沉降器 7压力为 1.5〜4xl05帕， 反应时间为 0.5~10秒， 催化剂与 烃油原料的重量比为 6~40。 反应油气和催化剂的混合物沿提升管上行 至提升管出口处后进入沉降器 7, 在沉降器 7 内反应油气与积炭的催 化剂分离。 反应油气经管线 8送入后续分离系统完成产物分离， 而反 应后积炭的催化剂进入汽提器 6。 汽提蒸汽和来自管线 14的抑制剂经 管线 5注入， 汽提蒸汽与积炭的催化剂逆流接触， 将积炭的催化剂所 携带的反应油气尽可能地汽提干净； 抑制剂经汽提器 6进入沉降器 7 抑制乙烯、 丙烯进一步发生二次转化反应， 之后随反应油气一同进入 产物分离系统。 汽提后的催化剂经待生剂输送管线 15送入再生器 18 烧焦再生。 含氧气体如空气经管线 17注入再生器 18， 再生烟气经管 线 19引出。 再生后的催化剂经再生剂输送管线 16返回提升管 4循环 使用。
下面通过实施例进一步说明本发明提供的方法， 但本发明并不因 此受到任何限制。 实施例中所使用的催化剂由中国石油化工股份有限公司催化剂齐 鲁分公司工业生产， 商品牌号为 MMC-2。 实施例中所用的原料 A为 丙烯浓度大于 99.9体％的纯丙烯气体， 原料 B 为一种减压瓦斯油， 其主要性质见表 1。 实施例 1
本实施例说明： 采用本发明提供的方法， 以一氧化碳为抑制剂时 低碳烯烃在小型固定流化床反应器内的催化反应活性情况。
实验以原料 A为原料， 采用间歇操作方式， 原料、 抑制剂和雾化 蒸汽经预热炉加热至 350°C左右后通过进料喷嘴进入流化床反应器底 部， 与热的催化剂接触进行催化转化反应。 反应产物和抑制剂与催化 剂分离后进入产物分离系统， 反应产物进一步分离成气体产物和液体 产物。 反应结束后进入汽提阶段， 由水蒸汽汽提出待生催化剂上吸附 的烃类产物。 汽提后向反应器内通入含氧气体进行待生催化剂的再 生， 催化剂再生后可以进行下一次反应。 实验的主要操作条件和结果 列于表 2。 实施例 Γ
本实施例说明： 反应过程中不注入抑制剂情况下低碳烯烃的催化 反应活性， 以进一步说明本发明的实施效果， 该实施例是发明人在实 验室发现的一种与常规认识不同的实验现象。
实验以原料 A为原料， 所用的反应器及主要实验步骤、 其它操作 条件与实施例 1相同， 主要操作条件和结果列于表 2。
将表 2中实施例 1和实施例 1，的实验结果进行对比后可以看出， 丙烯在常规催化转化制烯烃的反应条件下具有相当高的反应活性， 丙 烯转化反应转化率达 55.19 重％, 这一点与多数研究者的认识具有较 大的差别。 而本发明提出的方法可以大大抑制丙烯的二次转化反应， 实施例 1中丙烯的转化率下降 22.8个百分点。 实施例 2
本实施例说明： 采用本发明提供的方法， 以氢气为抑制剂时低碳 烯烃在小型固定流化床反应器内的催化反应活性情况。 实验以原料 A为原料， 所用的反应器及主要实验步骤与实施例 1 相同， 主要操作条件和结果列于表 2。 实施例 2'
本实施例说明： 反应过程中不注入抑制剂情况下低碳烯烃的催化 反应活性， 以进一步说明本发明的实施效果， 该实施例是发明人在实 验室发现的一种与常规认识不同的实验现象。
实验以原料 A为原料， 所用的反应器及主要实验步骤、 其它操作 条件与实施例 2相同， 主要操作条件和结果列于表 2。
将表 2中实施例 2和实施例 2，的实验结果进行对比后可以看出， 丙烯在常规催化转化制烯烃的反应条件下具有相当高的反应活性， 丙 烯转化反应转化率达 64.01 重％, 这一点与多数研究者的认识具有较 大的差别。 而本发明提出的方法可以大大抑制丙烯的二次转化反应， 实施例 2中丙烯的转化率下降 29.97个百分点。 实施例 3
本实施例说明： 采用本发明提供的方法， 以氨为抑制剂时低碳烯 烃在小型固定流化床反应器内的催化反应活性情况。
实验以原料 A为原料， 所用的反应器及主要实验步骤与实施例 1 相同， 主要操作条件和结果列于表 2。 从表 2可以看出， 丙烯的转化 率仅为 38.30重％。 实施例 4
本实施例说明： 采用本发明提供的方法， 当抑制剂在不同位置注 入时， 重质烃类催化转化制取乙烯和丙烯的情况。
实验以原料 B 为原料， 以甲醇为抑制剂， 在连续反应-再生操作 的中型提升管装置上进行催化转化实验。 该提升管的内径为 16毫米， 高度为 6米， 提升管反应段出口以上有一段流化床反应段， 该流化床 反应段的内径为 64亳米， 高度为 0.3米。
实验采用单程通过的操作方式， 抑制剂的注入位置为原料喷嘴。 温度为 700 °C左右的再生催化剂经再生斜管进入提升管反应段的底 部， 并在预提升蒸汽的作用下向上流动。 原料油经预热炉加热至 350 °c左右后与雾化水蒸汽和抑制剂混合后， 通过进料喷嘴依次进入到提 升管反应段和流化床反应段内， 与热的催化剂接触进行催化转化反 应。 反应产物、 抑制剂和水蒸汽以及待生催化剂从流化床反应段出口 进入到沉降器， 在沉降器内反应产物和抑制剂与催化剂快速分离， 反 应产物进一步分离成气体产物和液体产物， 而待生催化剂由重力作用 进入到汽提器， 汽提水蒸汽汽提出待生催化剂上吸附的烃类产物后通 过流化床反应段进入气固分离系统。 汽提后的待生催化剂进入到再生 器， 与加热过的空气接触进行再生。 再生后的催化剂在输送管线内用 水蒸汽汽提， 以除去再生催化剂吸附和携带的非烃气体杂质。 汽提后 的再生催化剂再返回到提升管反应段中循环使用。
实验的主要操作条件和结果列于表 3。 从表 3 可以看出， 乙烯、 丙烯产率分别高达 8.73重％和 29.30重％。 对比例
本对比例说明： 反应过程中不注入抑制剂情况下， 以重质烃类为 原料催化转化制取乙烯和丙烯的情况， 以进一步说明本发明的实施效 果。
实验以原料 B为原料， 所用的反应装置及主要实验步骤、 其它操 作条件与实施例 4相同， 主要操作条件和结果列于表 3。 实施例 4和 对比例中原料 B在提升管反应段入口处分压相等， 以保证原料的转化 不受分压变化所带来的影响。
将表 3中实施例 4和对比例的实验结果进行对比后可以看出， 在 现有石油烃催化转化制取低碳烯烃技术的基础之上， 本发明提供的方 法可以得到较高的乙烯、 丙烯产率， 比同等反应条件下不注入抑制剂 的对比例相比， 乙烯、 丙烯产率分别提高了 14.4%和 26.6%。 实施例 5
本实施例说明： 采用本发明提供的方法， 当抑制剂在不同位置注 入时， 重质烃类催化转化制取乙烯和丙烯的情况。
实验以原料 B为原料， 以氢气为抑制剂， 抑制剂的注入位置为汽 提蒸汽分布器。 实验所用的反应装置及主要实验步骤与实施例 4相同， 主要操作条件和结果列于表 3。 从表 3 可以看出， 乙烯、 丙烯产率分 别高达 8.73重％和 28.55重％。 实施例 6
本实施例说明： 采用本发明提供的方法， 当抑制剂在不同位置注 入时， 重质烃类催化转化制取乙烯和丙烯的情况。
实验以原料 B为原料， 以十氢萘为抑制剂， 抑制剂的注入位置为 预提升蒸汽分布器。 实验所用的反应装置及主要实验步骤与实施例 4 相同， 主要操作条件和结果列于表 3。 从表 3 可以看出， 乙烯、 丙烯 产率分别高达 8.15重％和 27.88重％。 实施例 7
本实施例说明： 采用本发明提供的方法， 以装置自产的干气为抑 制剂、 抑制剂循环使用并在原料喷嘴处注入时， 重质烃类催化转化制 取乙烯和丙烯的情况。
实验以原料 B为原料， 实验所用的反应装置及主要实验步骤与实 施例 4相同， 主要操作条件和结果列于表 3。 从表 3可以看出， 乙烯、 丙烯产率分别高达 8.29重％和 28.52重％。
原料油名称 B 密度（20°C ) ， 克 /厘米 3 0.8617 运动粘度（80 ) ， 亳米 秒 7.33 运动粘度（100Ό ) ， 亳米 2/秒 4.864 凝点， °C 42 笨胺点， C 105.3 分子量（计算） 391 残炭， 重％ 0.02
H/C摩尔比 1.895 碱性氮， ppm 206 元素组成
C, 重0 /« 86.3
H, 重0 /0 13.63
N, ppm 560
S, ppm 810 族組成， 重％
饱和烃 85.0 芳烃 12.0 胶质 3.0 沥青质 <0.1 金属含量， ppm
Ca -
Cu <0.1
Fe 2
Na 1.8
Ni <0.1
V <0.1 馏程， °C
初條点 286
5% 343 10% 368
30% 410
50% 437
70% 465
90% 498
95% 512 表 2
Figure imgf000014_0001
定义丙烯的重量百分转化率如下 重量百分转化率 (重 %)=丙烯珊量 中丙烯的重量 (g)-： 丙烯进料量 (g) 表 3
实施例 实施例 实施例 实施例 项目 对比例
4 5 6 7 操作条件
反应温度， °c 620 620 650 580 615 总反应时间， 秒 2.9 2.9 1.8 4.2 3.8 沉降器压力， 10s帕 2.7 2.7 2.1 1.9 2.3 催化剂与原料重量
20 20 10 30 15 比
抑制剂与原料重量
1.5 0 0.0045 5.0 0.1 比， ％
产品分布， 重％
裂化气 66.65 58.91 64.63 63.21 65.73 其中乙烯 8.73 7.63 8.73 8.15 8.29 丙婦 29.30 23.14 28.55 27.88 28.52 汽油 18.56 20.51 18.08 19.29 18.52 柴油 6.07 9.43 6.82 8.94 7.99 重油 2.30 3.69 2.37 3.14 3.79 焦炭 6.42 8.18 8.10 5.42 3.97

Claims

权 利 要 求
1、 一种增产低碳烯烃的催化转化方法， 烃油原料与催化转化催 化剂在包括一个或多个反应段的催化转化反应器内接触并反应， 其特 征是在反应过程中使烃油原料在抑制剂存在的情况下发生催化转化反 应， 将含或不含抑制剂的反应油气与反应后积炭的催化剂分离， 其中 反应油气经分离得到含有乙烯、 丙烯的目的产物， 积炭的催化剂经汽 提、 再生后返回反应段循环使用。
2、 按照权利要求 1 的方法， 其特征在于所述的烃油原料选自石 油烃油、 矿物油和合成油中的一种或一种以上的混合物， 其中石油烃 油选自 C4〜C6馏分、 汽油、 柴油、 減压瓦斯油、 焦化瓦斯油、 脱沥 青油、 加氢尾油、 常压渣油、 减压渣油和原油中的一种或一种以上的 混合物； 矿物油选自煤液化油、 油 、油和页岩油中的一种或一种以上 的混合物； 合成油为煤、 天然气或沥青经过 F-T合成得到的馏分油。
3、 按照权利要求 1 的方法， 其特征在于所述的催化转化催化剂 包括沸石、无机氧化物和任选的粘土，各组分的含量分别为：沸石 10 ~ 50重％、 无机氧化物 5 ~ 90重％、 粘土 0 ~ 70重。 /0。
4、 按照权利要求 3 的方法， 其特征在于所述的沸石选自平均孔 径小于 0.7納米的中孔沸石和任选的平均孔径大于 0.7纳米的大孔沸 石， 中孔沸石占沸石总重量的 25 ~ 100重％, 大孔沸石占沸石总重量 的 0 ~ 75重％。
5、按照权利要求 4的方法，其特征在于所述的中孔沸石选自 ZSM 系列沸石和 /或 ZRP 沸石， ZSM 系列沸石选自 ZSM-5、 ZSM-8、 ZSM-11、 ZSM-12、 ZSM-23, ZSM-35, ZSM-38、 ZSM-48 和其它类 似结构的沸石之中的一种或一种以上的混合物。
6、 按照权利要求 4 的方法， 其特征在于所述的大孔沸石选自由 稀土 Y、 稀土氢 Υ、 不同方法得到的超稳 Υ、 高硅 Υ构成的这組沸石 中的一种或一种以上的混合物。
7、 按照权利要求 1 的方法， 其特征在于所述的催化转化反应器 的反应段选自一个或一个以上的提升管、 一个或一个以上的流化床、 一个或一个以上的下行管、 提升管 +流化床、 提升管 +下行管、 下行 管 +流化床以及在它们基础上改进的型式， 其中提升管可以是等直径 的提升管也可以是各种变直径的提升管。
8、 按照权利要求 1 的方法， 其特征在于所述的抑制剂是或包含 具备供氢能力的物质、 具备还原能力的物质和能够吸附在酸性催化剂 活性中心上的物^中的一种或一种以上的混合物。
9、 按照权利要求 8 的方法， 其特征在于所述的具备供氢能力的 物质是或包含氢气、 四氢萘、 十氢萘、 催化裂化干气和焦化干气中的 一种或一种以上的混合物。
10、 按照权利要求 8的方法， 其特征在于所述的具备还原能力的 物质是或包含一氧化碳。
11、 按照权利要求 8 的方法， 其特征在于所述的能够吸附在酸性 催化剂活性中心上的物质是或包含甲醇、 乙醇、 氨和吡啶中的一种或 一种以上的混合物。
12、 按照权利要求 1或 8的方法， 其特征在于所述的抑制剂注入 位置包含烃油原料进料管线、 再生催化剂输送管线、 反应器的反应段、 用于使反应油气与积炭催化剂分离的沉降器和用于汽提积炭催化剂的 汽提器中的任一部分。
13、 按照权利要求 1或 8的方法， 其特征在于所述的抑制剂从反 应段的催化剂入口的下游注入。
14、 按照权利要求 1、 7或 8 的方法， 其特征在于所述的抑制剂 在多个反应段之间注入， 条件是所述反应器有多个反应段。
15、 按照权利要求 1、 7或 8 的方法， 其特征在于所述的抑制剂 在提升管与流化床之间注入， 条件是所述的催化转化反应器的反应段 为提升管 +流化床。
16、 按照权利要求 1、 7 或 8 的方法， 其特征在于所述的抑制剂 从变直径的提升管的变直径处注入， 条件是在催化转化反应器中所用 的反应段为变直径的提升管。
17、 按照权利要求 1或 8的方法， 其特征在于以烃油原料的重量 为计算基准， 所述的抑制剂与烃油原料的重量比为 0.001〜： 15重％。
18、 按照权利要求 17 的方法， 其特征在于以烃油原料的重量为 计算基准， 所述的抑制剂与烃油原料的重量比为 0.003〜10重％。
19、 按照权利要求 1或 8的方法， 其特征在于所述的抑制剂可以 由一点注入， 也可以由一点以上同时注入， 每点的注入量为抑制剂总 注入量的 0〜； 100重％。
20、 按照权利要求 1 的方法， 其特征在于反应条件为： 反应器最 后一个反应段的出口温度 500〜700°C， 用于使反应油气与积炭催化剂 分离的沉降器的压力 1.5〜4xl05帕， 反应时间 0.5〜10秒， 催化剂与烃 油原料的重量比 6〜40， 水蒸汽与烃油原料的重量比 0.1〜1： 1。
21、 按照权利要求 20 的方法， 其特征在于反应条件为： 反应器 最后一个反应段的出口温度 550〜650°C；， 用于使反应油气与积炭催化 剂分离的沉降器的压力 1.5〜3.5xlOs帕， 反应时间 1〜5 秒， 催化剂与 烃油原料的重量比 10〜30， 水蒸汽与烃油原料的重量比 0.2 0.6： 1。
22、 按照权利要求 1、 20和 21 中任一项的方法， 其特征在于所 述的催化转化反应器的反应段为提升管 +流化床， 所述抑制剂是甲 醇， 其在所述催化转化反应器中单程使用。
23、 按照权利要求 1、 20和 21 中任一项的方法， 其特征在于所 述的催化转化反应器的反应段为提升管 +流化床， 所述抑制剂是氢 气， 其在所述催化转化反应器中单程使用。
24、 按照权利要求 1、 20和 21 中任一项的方法， 其特征在于所 述的催化转化反应器的反应段为提升管 +流化床， 所述抑制剂是十氢 奈， 其在所述催化转化反应器中单程使用。
25、 按照权利要求 1、 20和 21 中任一项的方法， 其特征在于所 述的催化转化反应器的反应段为提升管 +流化床， 所述抑制剂是所述 催化转化反应器自产的干气， 其在所述催化转化反应器中循环使用。
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