JP4412886B2 - Catalytic cracking of petroleum hydrocarbons - Google Patents

Description

【００９１】
【表２】

【００９２】
【表３】

【００９３】
【表４】

【００９４】
【表５】

【００９５】
【表６】

【００９６】
【表７】

【図面の簡単な説明】
【図１】 触媒を供給するための単一の導管を有する二重管上昇流反応器の概略構造図である。
【図２】 触媒を供給するための単一の導管を有する二重管上昇流反応器における内管、外管および合流管の接合領域の概略構造図である。
【図３】 触媒を供給するための単一の導管を有する二重管上昇流反応器における内管および外管の供給ノズルの設定モードの概略図である。
【図４】 触媒を供給するための２つの導管を有する二重管上昇流反応器の概略構造図である。
【図５】 触媒を供給するための２つの導管を有する二重管上昇流反応器における内管、外管および合流管の接合領域の概略構造図である。
【図６】 二重管上昇流反応器を用いた石油炭化水素の接触分解処理の主要な流れ図である。
【図７】 二重管上昇流反応器を用いた石油炭化水素の接触分解処理の主要な流れ図である。
【図８】 二重管上昇流反応器を用いた石油炭化水素の接触分解処理の主要な流れ図である。
【図９】 二重管上昇流反応器を用いた石油炭化水素の接触分解処理の主要な流れ図である。
【図１０】 石油炭化水素のリレー分解処理の主な流れ図である。
【図１１】 石油炭化水素のリレー分解処理の主な流れ図である。
【符号の説明】
１ 触媒入口導管、２ 内管、３ 外管、５，６，７ 予備引上げ分配リング、８，９ 供給ノズル、１０ 固定部材。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to the catalytic cracking (catalytic cracking) treatment of petroleum hydrocarbons in the absence of hydrogen.
[0002]
[Prior art]
Although catalytic cracking has been developed for decades and has a relatively complete technical structure, refiners still not only meet increasingly stringent environmental laws and regulatory requirements, but also market requirements. We are constantly researching and researching to find a process that will provide a satisfactory economic benefit to the enterprise by responding to changing demand.
[0003]
USP 5043522 and USP 5846403 relate to improvements in conventional catalytic cracking processes, according to which a portion of the catalytic gasoline is fed to an upflow reactor upstream of the feed nozzle and is regenerated with high activity at high temperatures. The contact with the catalyst increases the yield of light olefins such as propylene and butylene, while improving the octane number of gasoline.
[0004]
CN 1279270A discloses a process for simultaneously increasing the yield of both liquefied petroleum gas and diesel oil. Even in this treatment, catalytic gasoline is supplied to the upflow reactor upstream of the feed nozzle and first contacts the regenerated catalyst and then reacts. This portion of reprocessed catalyzed gasoline is completely cracked at high temperatures under the condition that the catalyst to oil ratio is high, producing a large amount of liquefied petroleum gas. During this time, since only a small amount of coke is deposited on the catalyst, the activity of the catalyst is appropriately reduced to produce more diesel oil.
[0005]
USP 3894933 discloses a catalytic cracking process using two upflow reactors sharing a disengager. In this process, circulating gas oil is fed to the upflow reactor and contacts the regenerated catalyst, resulting in a conversion of less than 30%. The spent catalyst is fed to a separate upflow reactor and comes into contact with new feedstock and circulating heavy oil.
[0006]
CN 1069054A discloses a flexible and versatile catalytic cracking process for hydrocarbons. This process relates to two independent upflow reactors and two sedimentation separation systems attached to these upflow reactors. In the first upflow reactor, the light hydrocarbon is at a temperature of 600 to 700 ° C., the ratio of catalyst to oil is 10 to 40, the reaction time is 2 to 20 seconds, and the carbon content of the catalyst is 0.1 to 0.4. It contacts and reacts with the regenerated catalyst under conditions controlled in the weight percent range, and the spent catalyst is fed to the other riser to contact heavy hydrocarbons under conventional catalytic cracking conditions.
[0007]
Both USP 4820493 and CN 1174094A have a larger diameter of the pre-pumped portion of the upflow reactor, where the inner tube for transporting the catalyst is set coaxially to provide a contact effect between the oil and the catalyst. Improving and increasing the yield of the desired product. The catalyst transfer inner pipe is positioned at a position below the hydrocarbon oil supply nozzle.
[0008]
USP 4310489 and CN 1096047A both use a catalytic cracking unit with two upflow reactors. Here, one reactor is used to handle conventional catalytic cracking heavy feedstocks, and the other reactor is used for catalysts that reform low quality diesel oil or heavy gasoline fractions.
[0009]
In short, the catalytic conversion treatment for simultaneously treating light oil and heavy oil disclosed in the prior art can be basically divided into two categories. (1) One that uses a single upflow reactor to charge a light raw material upstream of the inlet of a heavy raw material, and (2) Two separate upflow reactors that use separate reactors to feed separate raw materials. To be processed. The first category of these processes requires little modification of the device. However, the reaction state of light oil is essentially fixed, and product distribution and product characteristics can hardly be improved by optimizing operating variables. The second category of these treatments overcomes the disadvantages of the first category, and the operating conditions of each upflow reactor are individually adjusted to perform each reaction under different conditions that match different feedstocks. Can be done. However, for the second processing category, both unit building and device rebuilding increase significantly. Furthermore, in actual industrial production, the operation becomes very difficult due to the complicated production process.
[0010]
[Problems to be solved by the invention]
The object of the present invention is to provide a double-tube ascending reactor that can provide hydrocarbon feedstocks with different characteristics under suitable reaction conditions and can clearly improve the product distribution and product properties of the catalytic cracking process. It is to provide a catalytic cracking treatment of petroleum hydrocarbons.
[0011]
Another object of the present invention is the relay cracking of petroleum hydrocarbons, where the catalytic cracking process not only has the desired ability to convert heavy oil and better product selectivity, but also simplifies the production process and is easy to operate. Is to provide processing.
[0012]
[Means for Solving the Problems]
The catalytic cracking process provided in the present invention includes the following steps.
[0013]
(1) An inlet conduit for a catalyst that flows upward under the action of pre-lifting media into the inner tube of the double tube upflow reactor and the annular space between the inner and outer tubes. Supplying from the step,
(2) A hydrocarbon raw material is supplied to the inner tube of the reactor and the annular space between the inner tube and the outer tube, and the hydrocarbon raw material comes into contact with the catalyst in the inner tube and the annular space, By forming a mixture with the catalyst so that the reaction of the hydrocarbon feedstock is carried out under catalytic cracking reaction conditions to form a reaction stream that flows upward along the wall of the vessel;
(3) The reaction flows from both the inner pipe and the annular space between the inner pipe and the outer pipe merge at the inlet of the merging pipe, and then enter the separation device via the merging pipe. Separating the hydrocarbon product stream from the spent catalyst; and
(4) The above reaction to further separate the hydrocarbon product stream into various products including gasoline, diesel oil and liquefied petroleum gas, remove and regenerate spent catalyst, and reuse the regenerated catalyst. Recirculating into the vessel.
[0014]
Another catalytic cracking process (ie, relay cracking process) provided in the present invention mainly includes the following steps.
[0015]
(1) sending the regenerated catalyst through the catalyst conduit to the bottom of the double-pipe upflow reactor, the catalyst flowing upward under the action of the pulling medium, and the regenerated catalyst 20-80 The weight percent flows into the inner tube, the remaining portion of the regenerated catalyst enters the annular space between the inner and outer tubes and flows upward under the action of the pre-pumping medium;
(2) The hydrocarbon raw material is supplied to the inner tube of the reactor and brought into contact with the catalyst therein to form a mixture of oil and catalyst, whereby the hydrocarbon raw material is reacted under catalytic cracking reaction conditions. Forming a reaction flow that flows upward along the vessel wall;
(3) The reaction flow from the inner pipe and the regenerated catalyst (flow) from the annular space join together in the joining pipe, and the reaction steam continuously reacts under catalytic cracking conditions, and the resulting reaction stream joins Introducing into the separator via a tube, where the hydrocarbon product stream is separated from the spent catalyst; and
(4) The above reactor to further separate the hydrocarbon product stream into various products including gasoline, diesel oil and liquefied petroleum gas, remove and regenerate spent catalyst, and reuse the regenerated catalyst. Step to recirculate into.
[0016]
Compared with the prior art, the advantageous effects of the present invention are mainly embodied in the following aspects.
[0017]
The process provided by the present invention is simple to equip and flexible in operation. Not only can the reactions of heavy oil and light oil be carried out separately in their respective reaction zones, but also the reaction conditions can be flexibly adjusted according to the physicochemical properties and the mass flow rates of the different feedstocks, so product distribution and production It is possible to create favorable conditions for improving the quality of objects.
[0018]
The treatment provided in the present invention can flexibly constitute a plurality of production schemes such as a gasoline scheme, a diesel oil scheme, a liquefied petroleum gas scheme, a light olefin scheme, and the like. Thus, oil refineries can adjust product distribution patterns with ease by using the process of the present invention in response to fluctuations in market demand to obtain more beneficial economic benefits.
[0019]
The process of the present invention can clearly improve the distribution of catalytic cracking products, reduce the yield of dry gas and coke, and increase the yield of valuable products such as liquefied petroleum gas, gasoline and / or diesel oil. be able to.
[0020]
Furthermore, the treatment provided in the present invention can also improve product quality and reduce environmental pollution caused by petroleum products. These treatments reduce the olefin content of gasoline, increase the octane number of gasoline, lower the freezing point of diesel oil, increase the sensitivity of diesel oil to flow improvers, increase the stability of diesel oil, On the other hand, these treatments have been found to have a particular effect in reducing the content of impurities such as sulfur and nitrogen in gasoline and diesel oil.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
A double pipe upflow reactor is used in both the catalytic cracking process of petroleum hydrocarbons and the catalytic relay cracking process of petroleum hydrocarbons of the present invention. This double tube upflow reactor may have a single conduit or two conduits for feeding the catalyst, or other reactors having a similar structure. The structure of the double pipe upflow reactor will be described in detail with reference to the drawings.
[0022]
In the present invention, a double pipe upflow reactor having a single conduit for supplying a catalyst has the structure shown in FIG. This reactor mainly includes the following members. Regenerated catalyst inlet conduit 1, inner tube 2, outer tube 3, merge tube 4, pre-lifting distribution rings 5, 6 and 7, and feed nozzles 8 and 9. Here, the inner tube 2 and the outer tube 3 are coaxial, and the ratio of the sectional area of the inner tube to the sectional area of the annular space between the inner tube and the outer tube is 1: 0.1 to 10, preferably 1. : The lower end of the inner tube 2 is positioned at a position above the inlet of the regenerated catalyst, and the length of the inner tube is 10 to 70% of the total length of the reactor, preferably 20 to 60%, one end of the merging pipe 4 is connected to the upper end of the outer pipe 3, the other end is connected to a gas / solid separator, and the ratio of the cross-sectional area of the merging pipe 4 and the inner pipe 2 is 1: 0. 2 to 0.8, the pre-lift distribution rings 5, 6 and 7 are located at the bottom of each of the reactor, inner and outer tubes. A plurality of fixing members 10 are installed. For example, 2-12 presser wires or pull rods may be provided between the inner and outer tubes depending on the specific size and design requirements of the reactor.
[0023]
In a double tube upflow reactor having a single conduit for feeding catalyst, the distance from the upper end of the inner tube (ie, the outlet end of the inner tube) to the outlet end of the merged tube is 1-30 meters (ie, The total length of the junction tube), preferably 2 to 20 meters. Various types of joining modes among the inner tube, the outer tube, and the joining tube can be set according to requirements. FIG. 2 illustrates four examples of bonding modes in the present invention, but is not intended to limit the present invention.
[0024]
As shown in FIG. 2, in Example A, the upper end of the inner tube has a straight tube shape, and the outer tube also has a straight tube shape. The inner diameters of the merge pipe and the outer pipe are the same. The inner diameter of the inner tube is D1, and the inner diameter of the confluence tube is D2, and D1: D2 = 0.4 to 0.9: 1.
[0025]
As shown in FIG. 2, in Example B, the diameter of the upper outlet portion of the inner tube is widened, the outer tube is a straight tube, and the confluence tube and the outer tube have the same inner diameter. The inner diameter of the inner tube is D1, and the inner diameter of the confluence tube is D2. The ratio of the height H1 of the upper outlet portion of the inner tube to the inner diameter D1 of the inner tube is 0.5-3: 1. The spread angle a of the upper outlet portion of the inner tube is 5 to 30 °.
[0026]
As shown in FIG. 2, in Example C, the diameter of the upper outlet portion of the inner tube is widened, and the outer tube is connected to the merging tube after the diameter is reduced. The inner diameter of the inner tube is D1, and the inner diameter of the confluence tube is D2. The ratio between the height H2 of the upper outlet portion of the inner tube and the inner diameter D1 of the inner tube is 0.5-3: 1. The spread angle b of the upper outlet portion of the inner tube is 5 to 30 °. The bottom end of the narrowed portion of the outer tube is positioned between 1.0D2 above the inner tube outlet and 1.0D2 below the inner tube outlet, and the convergence angle c is 10 to 60 °. The ratio between the height H3 of the narrowed portion of the outer tube and the inner diameter D2 of the merged tube is 0.5 to 3.0: 1.
[0027]
As shown in FIG. 2, in Example D, the upper end of the inner tube has a straight tube shape, and the outer tube is connected to the merging tube after the diameter is reduced. The inner diameter of the inner tube is D1, and the inner diameter of the confluence tube is D2. The bottom end of the narrowed portion of the outer tube is positioned between 1.0D2 above the inner tube outlet and 1.0D2 below the inner tube outlet, and the convergence angle d is 5 to 45 °. The ratio between the height H4 of the narrowed portion of the outer tube and the inner diameter D2 of the merged tube is 0.5 to 3.0: 1.
[0028]
There are three designs for the widened, equal and narrowed diameters of the lower end of the inner tube in a double tube upflow reactor with a single conduit for feeding the catalyst. Can be used. For example, in FIG. 3, the ratio of the height H5 of the inlet portion of the lower part of the inner tube to the inner diameter D1 of the inner tube is 0.5-3: 1, and the spread angle e is -30-30 °. For the lower end of the outer tube, three types of designs for wide, equal and narrow diameters can be used, the specific design concept here is the conventional catalytic cracking upflow This is the same as the design of the preliminary pull-up portion in the reactor.
[0029]
As shown in FIG. 1, the feed nozzle 8 of the double pipe upflow reactor having a single conduit for feeding the catalyst is installed in the lower part of the inner pipe at 5-30% of its total length. Can be done. Also, two to four layers of supply nozzles can be set along the inner tube. Alternatively, as shown in FIG. 3, the feed nozzle can be set along the central axis of the reactor so that it passes 0.1-3.0 meters into the inner tube after passing through the lower portion of the outer tube. The supply nozzle 9 can be set in the lower part of the outer tube at a location 5 to 30% of its total length. Also, two to four layers of supply nozzles can be set in the vertical direction of the outer tube. Feed nozzles 8 and 9 can be used in any form that is advantageous for uniformly dispersing the hydrocarbon feedstock. The supply nozzles 8 or 9 may be composed of 2 to 12 supply nozzles arranged uniformly along the circumferential direction. In order to create conditions for injecting coolant, a coolant nozzle can be set in the junction tube. In short, a relatively flexible supply mode can be used and supply injection at multiple points can be performed in the inner and outer tubes.
[0030]
A double tube upflow reactor having two conduits for supplying catalyst has the structure shown in FIG. This reactor mainly includes the following members. Catalyst inlet conduits 21 and 22, inner tube 35, outer tube 36, merge tube 38, pre-lift distribution rings 31 and 33, and feed nozzles 32 and 34. Here, the inner tube 35 and the outer tube 36 are coaxial, and the ratio of the cross-sectional area of the inner tube and the cross-sectional area of the annular space between the inner tube and the outer tube is 1: 0.1 to 10, preferably Is 1: 0.1-2. The catalyst inlet conduit 21 is connected to the lower end of the inner tube 35, which has a length of 10 to 70%, preferably 15 to 50% of the total length of the reactor. The distance from the lower end of the outer tube 36 to the lower end of the inner tube 35 is 2 to 20%, preferably 5 to 15% of the total length of the reactor. The catalyst inlet conduit 22 is connected to the lower end of the outer tube 36. One end of the joining pipe 38 is connected to the upper end of the outer pipe 36, and the other end is connected to the gas / solid separation device. The ratio of the cross-sectional area of the junction pipe 38 and the inner pipe 35 is 1: 0.2 to 0.8, preferably 1: 0.3 to 0.7. Pre-lift distribution rings 31 and 33 are positioned at the bottom of the inner tube and the bottom of the annular space between the inner and outer tubes, respectively. Feed nozzles 32 and 34 are located in the lower portions of the inner and outer tubes, respectively. A plurality of fixing members 30 are provided, and for example, depending on the specific size and technical requirements of the reactor, 2-12 presser wires or tension bars may be provided between the inner and outer tubes.
[0031]
In a double-tube upflow reactor having two conduits for supplying catalyst, the distance from the upper end of the inner tube (ie, the outlet end of the inner tube) to the outlet end of the merged tube (ie, the total length of the combined tube) is zero. .5 to 20 meters, preferably 1 to 10 meters. It is desirable to optimize the inner diameter of the merging pipe according to the linear velocity of the oil gas in the merging pipe, and the linear velocity of the oil gas in the merging pipe is 0.5 to 2.0 times the linear velocity at the inner pipe outlet, preferably Should be 0.8-1.2 times. The initial apparent linear velocity of the preliminary pulling medium is 0.3 to 8 m / s in the inner tube, and the apparent linear velocity of the preliminary pulling medium is 0.2 to 10 m / s in the outer tube.
[0032]
The connection region of the inner tube, the outer tube and the merge tube can be used in various ways depending on the requirements. FIG. 5 shows an example of four modes. However, there is no intention to limit the mode used for the reactor.
[0033]
As shown in FIG. 5, in Example A1, the upper end of the inner tube has a straight tube shape, and the outer tube also has a straight tube shape. The inner diameters of the merge pipe and the outer pipe are equal. The inner diameter of the inner tube is M1, and the inner diameter of the merged tube is M2, and M2: M1 = 1.5 to 5: 1.
[0034]
As shown in FIG. 5, in Example B1, the upper outlet portion of the inner tube has a larger diameter, the outer tube is a straight tube, and the inner diameters of the merge tube and the outer tube are equal. The inner diameter of the inner tube is M1, and the inner diameter of the merge tube is M2. The ratio between the height N1 of the upper outlet portion of the inner tube and the inner diameter M1 of the inner tube is 0.5-3: 1. The spread angle a1 of the upper outlet portion of the inner tube is 5 to 30 °.
[0035]
As shown in FIG. 5, in Example C1, the upper outlet portion of the inner tube has a larger diameter, and the outer tube is connected to the merging tube after the diameter has decreased. The inner diameter of the inner tube is M1, and the inner diameter of the merge tube is M2. The ratio between the height N2 of the upper outlet portion of the inner tube and the inner diameter M1 of the inner tube is 0.5-3: 1. The spread angle b1 of the upper outlet portion of the inner tube is 5 to 30 °. The bottom end of the narrowed portion of the outer tube is positioned between 1.0M2 above the inner tube outlet and 1.0M2 below the inner tube outlet. The ratio between the height N3 of the narrowed portion of the outer tube and the inner diameter M2 of the merged tube is 0.5 to 3.0: 1.
[0036]
As shown in FIG. 5, in Example D1, the upper end of the inner tube has a straight tube shape, and the outer tube is connected to the junction tube after the diameter is reduced. The inner diameter of the inner pipe is M1, and the inner diameter of the merge pipe is M2. The bottom end of the narrowed portion of the outer tube is positioned between 1.0M2 above the inner tube outlet and 1.0M2 below the inner tube outlet, and the convergence angle d1 is 5 to 45 °. The ratio between the height N4 of the narrowed portion of the outer tube and the inner diameter M2 of the merged tube is 0.5 to 3.0: 1.
[0037]
The design of the lower ends of both the inner and outer pipes in a double pipe upflow reactor with two conduits for feeding the catalyst is basically the same as the design of the pre-lift section in the conventional catalytic cracking upflow reactor. The same as above. The design of the pre-lift distribution rings 31 and 33 is also basically the same as in the conventional catalytic cracking process.
[0038]
In a double tube upflow reactor having two conduits for supplying catalyst, the feed nozzle 32 is set at a position 5-30% of the total length of the inner tube along the lower part of the inner tube. The supply nozzle 34 is set at a position 5 to 30% of the entire length of the outer tube along the lower portion of the outer tube. The feed nozzles 32 and 34 may be used in any form that is advantageous for uniformly dispersing the hydrocarbon feedstock. Both supply nozzles 32 and 34 may consist of 2 to 12 supply nozzles, which should be uniformly arranged along the circumferential direction.
[0039]
In the process provided in the present invention, the catalyst supplied to the inner pipe of the double pipe upflow reactor and the annular space between the inner pipe and the outer pipe via the catalyst inlet conduit is the same. May be different. Specifically, the catalyst supplied to the inner tube of the double tube upflow reactor and the annular space between the inner tube and the outer tube may be a catalyst regenerated from the regenerator at a high temperature. These catalysts can also be a mixture of regenerated catalyst and spent catalyst and / or semi-regenerated catalyst. Alternatively, the regenerated catalyst may be fed to the inner tube of the double tube upflow reactor, and the semi-regenerated catalyst or spent catalyst or mixture thereof is between the inner tube and the outer tube. It may be supplied to the annular space and vice versa. In short, the catalyst supplied to the catalyst inlet conduit can be comprehensively reviewed and flexibly reconfigured depending on the unit conditions, feed characteristics and requirements for the desired product. Furthermore, the catalyst to be fed to the double-pipe upflow reactor can be cooled via a catalyst cooler, or the regenerated catalyst and spent catalyst and / or semi-regenerated catalyst can be mixed in a catalyst mixing vessel. After being thoroughly mixed in, it may be fed to the double tube upflow reactor via the catalyst inlet conduit.
[0040]
The catalyst used in the present invention may be any catalyst suitable for catalytic cracking treatment, and its active component contains Y-type or HY-type zeolite, rare earth and / or rare earth and / or phosphorus. Or it contains or does not contain phosphorus. It is at least one zeolite selected from the group consisting of ultrastable Y-type zeolite, ZSM-5 group zeolite having a pentasil structure or high silica zeolite, β zeolite, ferrierite, and amorphous alumina-silica catalyst. Two different types of catalysts can be used in the inner tube and the annular space between the inner tube and the outer tube.
[0041]
In the process provided in the present invention, the bottom of the double tube upflow reactor, the bottom of the inner tube, and the bottom of the annular space between the inner tube and the outer tube are each provided with a pre-pumping medium inlet. . Steam, a dry gas, or a mixture thereof can be used as the preliminary pulling medium. The apparent linear velocity of the preliminary pulling gas in the inner tube is initially 0.3 to 6.0 m / s, and the apparent linear velocity of the preliminary pulling gas in the annular space between the inner tube and the outer tube is 0. 2 to 8.0 m / s.
[0042]
The hydrocarbon raw material supplied to the inner pipe and the annular space between the inner pipe and the outer pipe is gas hydrocarbon, refinery gas, primary treated gasoline fraction, secondary treated gasoline fraction, primary treated diesel oil Fractions, secondary treated diesel oil fractions, straight-run gas oil, coke gas oil, deasphalted oil, hydrofined oil, hydrocracked tail oil, vacuum residue, and their It can be selected from the group consisting of mixtures. The hydrocarbon feed supplied to the inner pipe is straight-run gas oil, coke gas oil, deasphalted oil, hydrofound oil, hydrocracked tail oil, vacuum residue, atmospheric residue, and mixtures thereof. Preferably it is selected from the group consisting of The hydrocarbon feed supplied to the annular space between the inner and outer pipes is gaseous hydrocarbon, refinery gas, primary treated gasoline fraction, secondary treated gasoline fraction, primary treated diesel oil fraction, It is preferably selected from the group consisting of secondary treated diesel oil fractions and mixtures thereof.
[0043]
The reaction conditions of the hydrocarbon raw material in the inner pipe are as follows. Reaction temperature 460-580 ° C, preferably 480-550 ° C, reaction pressure 0.1-0.6 MPa, preferably 0.2-0.4 MPa, ratio of catalyst to oil (weight ratio of catalyst to raw material) 3-15 , Preferably 4 to 10, oil gas residence time in the inner pipe 1.0 to 10 seconds, preferably 1.5 to 5.0 seconds, catalyst temperature 620 to 720 ° C. before contact with hydrocarbon feedstock, preferably 650 ~ 700 ° C, atomization (spray) steam volume 1-20 wt% (based on hydrocarbon feed), preferably 2-15 wt%.
[0044]
The reaction conditions of the hydrocarbon raw material in the annular space between the inner pipe and the outer pipe are as follows. Reaction temperature 300-680 ° C., preferably 400-600 ° C., reaction pressure 0.1-0.6 MPa, preferably 0.2-0.4 Mpa, ratio of catalyst to oil 2-30, preferably 4-20, oil Gas residence time 0.5 to 20 seconds, preferably 1 to 15 seconds, atomization vapor amount 1 to 20% by weight (based on hydrocarbon raw material), preferably 1 to 15% by weight. The reaction conditions of the hydrocarbon feed in the annular space between the inner and outer tubes can be further optimized in light of the characteristics of the hydrocarbon feed and the requirements of the desired product. When liquefied petroleum gas or light olefin is the main target product, relatively severe reaction conditions may be employed. For example, the reaction temperature is 530 to 680 ° C., the ratio of the catalyst to oil is 8 to 30, and the oil gas residence time is 5 to 20 seconds. When gasoline and / or diesel oil is the main target product, relatively mild operating conditions should be employed. For example, the reaction temperature is 300 to 540 ° C., the ratio of catalyst to oil is 2 to 8, and the oil gas residence time is 1 to 5 seconds.
[0045]
The reaction vapor in both the inner tube and the annular space between the inner tube and the outer tube is mixed at the inlet of the merging tube and then continues to react in the merging tube. Here, the reaction time is 0.1 to 3.0 seconds, and the reaction pressure, temperature, ratio of catalyst to oil, and the like depend on the reaction conditions of the inner tube and the annular space. Usually, the reaction temperature is 450 to 600 ° C., the ratio of catalyst to oil is 4 to 12, the reaction pressure is 0.1 to 0.6 MPa, and the weight ratio of steam to hydrocarbon feedstock is 0.01 to 0.15: 1. It is.
[0046]
The processing provided in the present invention is further described below in conjunction with the drawings, but is not limited.
[0047]
As shown in FIG. 6, the catalyst is fed via the catalyst inlet conduit 1 to the bottom of a double-pipe upflow reactor having a single conduit for catalyst feed and is moved upwards by the action of a pre-pumping medium. Flowing. Part of the catalyst (eg 20 to 80% by weight of the catalyst) flows into the inner tube 2 and the rest of the catalyst enters the annular space between the inner tube 2 and the outer tube 3, both of which are pre-pumping media It continues to flow upward by action. The hydrocarbon feed is supplied to the inner tube and the annular space between the inner tube and the outer tube via nozzles 8 and 9, respectively, and is brought into contact with the catalyst. Both of these reaction streams continue to flow upward along the vessel wall. The reaction flow from the inner tube and the reaction flow from the annular space between the inner tube and the outer tube merge at the inlet of the merge tube 4, and then the mixed flow is passed through the merge tube and the high-speed gas / solid separator. Into the regenerator 12 where the hydrocarbon product stream is separated from the spent catalyst. The separated hydrocarbon product stream then enters a subsequent separation system 14 where it is further separated into various products. The spent catalyst falls into the remover 13, where the reaction oil gas joined by the catalyst is removed by the action of steam. The removed catalyst is introduced into the regenerator 15, and coke is heated and removed with air. The regenerated catalyst is recycled to the reactor for reuse.
[0048]
As shown in FIG. 7, the catalyst is fed via the catalyst inlet conduit 1 to the bottom of a double-pipe upflow reactor having a single conduit for catalyst feed and is moved upward by the action of the pre-pumping medium. Flowing. Part of the catalyst (eg 20 to 80% by weight of the catalyst) flows into the inner tube 2 and the rest of the catalyst enters the annular space between the inner tube 2 and the outer tube 3, both of which are pre-pumping media It continues to flow upward by action. The hydrocarbon feed is fed into the reactor inner tube and the annular space between the inner and outer tubes via nozzles 8 and 9, respectively, and is brought into contact with the catalyst. These reaction streams continue to flow upward along the vessel wall. The reaction flow from the inner tube and the reaction flow from the annular space between the inner tube and the outer tube merge at the inlet of the merge tube 4, and the mixed flow passes through the merge tube and the gas / solid high-speed separator. The releaser 12 is entered where the hydrocarbon product stream is separated from the spent catalyst. The separated hydrocarbon product stream enters the subsequent separation system 14 and is further separated into various products, the spent catalyst falls into the remover 13, and the reaction oil gas joined by the catalyst is vaporized. Removed by action. The removed catalyst is supplied to the regenerator 15 so that the coke is heated and removed with air, and then the regenerated catalyst is introduced into the mixing vessel 16 and mixed with the used catalyst and / or the semi-regenerated catalyst. . The mixed catalyst is recycled to the reactor for reuse.
[0049]
As shown in FIG. 8, the regenerated catalyst enters the inner pipe 35 and the annular space between the inner pipe 35 and the outer pipe 36 in a double pipe upflow reactor having two conduits for catalyst supply. , Supplied through the catalyst inlet conduits 21 and 22 respectively, and flows upward by the action of the preliminary pulling medium. The hydrocarbon feed is supplied to the inner tube and the annular space between the inner and outer tubes via nozzles 32 and 34, respectively, and is brought into contact with the catalyst. These reaction streams flow upward along the vessel wall. The reaction flow from the inner tube and the reaction flow from the annular space between the inner tube and the outer tube merge at the inlet of the merge tube 38, and the mixed flow passes through the merge tube and the high-speed gas / solid separator. Enters releaser 12. In the eductor, the hydrocarbon product stream is separated from the spent catalyst. The separated hydrocarbon product stream enters the subsequent separation system 14 and is further separated into various products. The spent catalyst falls into the remover 13, where the reaction oil gas joined by the catalyst is removed by the action of steam. The removed catalyst is introduced into the regenerator 15 and the coke is heated off with air, after which the regenerated catalyst is recycled to the reactor for reuse.
[0050]
As shown in FIG. 9, the regenerated catalyst is supplied to the bottom of the inner pipe 35 of the double pipe upflow reactor via the catalyst inlet conduit 21 and flows upward by the action of the preliminary pulling medium. A portion of the spent catalyst flows into the annular space between the inner tube 35 and the outer tube 36 via the catalyst inlet conduit 22 and flows upward by the action of the preliminary pulling medium. The hydrocarbon feed is supplied to the inner tube and the annular space between the inner and outer tubes via nozzles 32 and 34, respectively, and is brought into contact with the catalyst. These reaction streams flow upward along the vessel wall. The reaction flow from the inner tube and the reaction flow from the annular space between the inner tube and the outer tube merge at the inlet of the merge tube 38, and the mixed flow is released through the merge tube and the high-speed gas / solid separator. Enter 12. In the eductor, the hydrocarbon product stream is separated from the spent catalyst. The separated hydrocarbon product stream then enters the subsequent separation system 14 where it is further separated into various products, where the spent catalyst falls into the remover 13 where the reaction oil gas joined by the catalyst. Is removed by the action of steam. A part of the used catalyst after the removal is supplied to the regenerator 15, the coke is heated and removed with air, and the regenerated catalyst is recycled to the bottom of the inner pipe and reused. The remainder of the spent catalyst is directly recycled to the bottom of the annular space between the inner and outer tubes and reused without regenerating treatment.
[0051]
In addition to the above-described flow charts shown in FIGS. 6-9, according to the process provided in the present invention, the regenerated catalyst, spent catalyst and semi-regenerated catalyst to be fed to the reactor, or of them Any two combinations can be fed to the bottom of the double tube upflow reactor via the catalyst inlet conduit after being cooled by the catalyst cooler.
[0052]
The reactor, catalyst, feedstock and operating conditions used in the petroleum hydrocarbon relay cracking process provided in the present invention are those in the petroleum hydrocarbon catalytic cracking process using the double pipe upflow reactor described above. Substantially the same, the difference being that the hydrocarbon feed is fed only to the inner tube of the double tube upflow reactor and not to the annular space between the inner and outer tubes. Accordingly, the petroleum hydrocarbon relay cracking process differs from the petroleum hydrocarbon catalytic cracking process using the double pipe upflow reactor described above in terms of feedstock and operating conditions.
[0053]
The hydrocarbon raw material supplied to the inner pipe is gas hydrocarbon, refinery gas, primary treatment gasoline fraction, secondary treatment gasoline fraction, primary treatment diesel oil fraction, secondary treatment diesel oil fraction, straight run gas Selected from the group consisting of oils, coke gas oils, de-alphalt oils, hydrofound oils, hydrocracked tail oils, vacuum gas oils, vacuum residue, atmospheric residue, and mixtures thereof.
[0054]
The reaction of the hydrocarbon raw material in the inner tube is performed at a reaction temperature of 480 to 700 ° C., preferably 500 to 680 ° C., a reaction pressure of 0.1 to 0.6 MPa, preferably 0.2 to 0.4 MPa, and a catalyst for oil. The ratio is 3 to 30, preferably 4 to 25, the oil gas residence time in the inner pipe is 1.0 to 10 seconds, preferably 1.5 to 5.0 seconds, and the catalyst temperature before contact with the hydrocarbon raw material is 620 It is carried out under the conditions of ˜800 ° C., preferably 640 to 750 ° C., and the amount of atomization vapor (based on raw materials) of 1 to 45% by weight, preferably 2 to 35% by weight.
[0055]
The reaction conditions of hydrocarbons in the junction tube are as follows: the reaction temperature is 490 to 720 ° C., preferably 500 to 700 ° C., the reaction pressure is 0.1 to 0.6 MPa, preferably 0.2 to 0.4 MPa, and the catalyst for oil The ratio is 4 to 40, preferably 5 to 30, the oil gas residence time in the junction pipe is 0.5 to 10 seconds, preferably 1.0 to 5.0 seconds, and the ratio of steam to oil is 3 to 45 weights. %, Preferably 5 to 35% by weight. The ratio of steam to oil means the weight ratio of steam to hydrocarbon feedstock.
[0056]
In the following, the relay cracking process of petroleum hydrocarbon will be further described in combination with the drawings, but is not limited thereto.
[0057]
As shown in FIG. 10, the regenerated catalyst is fed through the catalyst inlet conduit 1 to the bottom of a double tube upflow reactor having a single conduit for catalyst supply, and is acted upon by the action of a pre-pumping medium. Flows upward. 20-80% by weight of the catalyst flows into the inner tube 2 and the remainder of the catalyst enters the annular space between the inner tube 2 and the outer tube 3, both of which continue to flow upwards by the action of the pre-drawing medium. . The hydrocarbon feed is supplied to the inner tube of the reactor via the nozzle 8 and brought into contact with the catalyst. This reaction stream continues to flow upward along the vessel wall. The reaction flow from the inner tube merges with the regenerated catalyst (steam) from the annular space between the inner tube and the outer tube at the inlet of the merge tube 4, and then the mixed reaction stream is combined with the merge tube and It enters the liberator 12 via a high speed gas / solid separator where the hydrocarbon product stream is separated from the spent catalyst. The separated hydrocarbon product stream enters the subsequent separation system 14 and is further separated into various products. The spent catalyst falls into the remover 13, where the reaction oil gas joined by the catalyst is removed by the action of steam. The removed catalyst is introduced into the regenerator 15, and coke is heated and removed with air. The regenerated catalyst is recycled to the reactor for reuse.
[0058]
As shown in FIG. 11, the regenerated catalyst enters the inner pipe 35 and the annular space between the inner pipe 35 and the outer pipe 36 in a double pipe upflow reactor having two conduits for catalyst supply. , Supplied through the catalyst inlet conduits 21 and 22 respectively, and flows upward by the action of the preliminary pulling medium. The hydrocarbon feed is supplied to the inner tube of the reactor via the nozzle 32 and brought into contact with the catalyst. The reaction stream flows upward along the vessel wall. The reaction flow from the inner pipe merges with the regenerated catalyst (steam) from the annular space between the inner pipe 35 and the outer pipe 36 at the inlet of the merge pipe 38, and then the mixed flow is the merge pipe and It enters the releaser 12 via a high-speed gas / solid separator. In the releaser, the hydrocarbon product stream and spent catalyst are separated. The separated hydrocarbon product stream enters the subsequent separation system 14 and is further separated into various products. The spent catalyst falls into the remover 13, where the reaction oil gas joined by the catalyst is removed by the action of steam. The removed catalyst is introduced into the regenerator 15 where the coke is heated off with air and the regenerated catalyst is recycled to the reactor for reuse.
[0059]
In the petroleum hydrocarbon relay cracking process as well as those shown in FIG. 10 and FIG. 11 described above, the regenerated catalyst to be supplied to the reactor is cooled by the catalyst cooler and then double pipe upflow reaction. Can be fed to the bottom of the vessel.
[0060]
The following examples further illustrate the processes provided in the present invention, but are not intended to be limiting.
[0061]
The catalyst used in each example is a commercial product of the trademark LV-23 manufactured by Catalyst Factory, Lan Zhou Petrochemical Corp., the main properties of which are shown in Table 1. The hydrocarbon raw material used in each example is a DaQing VGO mixed with 30% by weight of VR. Table 2 shows the characteristics. The test equipment used in each example is a double pipe upflow reactor employing a pilot FCC unit.
[0062]
Example 1
This example shows the test results obtained when light oil was produced as the main target product using the process provided in the present invention.
[0063]
The main steps of the test are as follows: The raw materials shown in Table 1 and the recirculated oil of this unit are mixed. The mixed oil is heated in the preheating furnace, supplied to the inner pipe of the double pipe upflow reactor, and flows from the regenerator. And contacted with the regenerated catalyst pulled up by the pre-pumping medium. The cracked gas generated in this unit was supplied to the annular space between the inner and outer tubes and contacted with the regenerated catalyst therein. The reaction flow in the inner tube and the reaction flow in the annular space respectively rose along the wall of the vessel and then mixed with each other in the confluence tube to continue the reaction and enter the freezer. In the eductor, the hydrocarbon product stream was separated from the spent catalyst and then entered into the subsequent diversion system via the oil gas pipeline and further diverted to various products. Each of these products was weighed. The spent catalyst was removed with steam and then introduced into the regenerator where the coke was heated off with air. The regenerated catalyst was recycled to the reactor for reuse.
[0064]
The main operating conditions, product distribution and main product characteristics are shown in Table 3, Table 4 and Table 5, respectively. From Tables 4 and 5, when diesel oil is produced as the main target product, the gasoline + diesel oil yield reaches a maximum of 77.80% by weight, and the total yield of liquid product is 89.96. It can be seen that dry gas and coke can be obtained in lower yields.
[0065]
Example 2
This example shows the test results obtained when liquefied petroleum gas was produced as the main target product using the process provided in the present invention.
[0066]
The main steps of the test are as follows: The raw materials shown in Table 1 were heated in a preheating furnace, then fed into the inner tube of a double tube upflow reactor and contacted with a regenerated catalyst that flowed in from the regenerator and pulled up with a pre-pumping medium. . The light oil (gasoline + diesel oil) produced in this unit having a distillation range lower than 350 ° C. was supplied to the annular space between the inner pipe and the outer pipe, and contacted with the regenerated catalyst therein. The reaction flow from the inner tube and the reaction flow from the annular space respectively rose along the wall of the vessel, mixed with each other in the merge tube and continued to react, and then entered the releaser. In the eductor, the hydrocarbon product stream was separated from the spent catalyst and then entered the subsequent diversion system via the oil gas pipeline and further diverted to various products. Each of these products was weighed. The spent catalyst was removed with steam and then introduced into the regenerator where the coke was removed by heating with air. The regenerated catalyst was recycled to the reactor for reuse.
[0067]
The main operating conditions are shown in Table 3, the product distribution is shown in Table 4, and the main product properties are shown in Table 5. From Tables 4 and 5, when liquefied petroleum gas is produced as the main target product, the yield of liquefied petroleum gas can reach 29.46% by weight, and the total yield of liquid product is 86.65. It can be seen that dry weight and coke can be obtained in lower yields, which can reach wt%.
[0068]
Example 3
This example shows the test results obtained when gasoline was produced as the main target product using the process provided in the present invention.
[0069]
The main steps of the test are as follows: The raw material shown in Table 1 and the recirculated oil produced in this unit are mixed, and the mixed oil is heated in a preheating furnace and supplied to the inner pipe of the double pipe upflow reactor. And was contacted with the regenerated catalyst that had flowed in and lifted with the pre-pumping medium. Coke gasoline (density 0.7316 g / cm ^Three RON = 58.8, MON = 65.4, olefin content 37.49 wt%) was fed to the annular space between the inner and outer tubes and contacted with the regenerated catalyst. The reaction flow in the inner tube and the reaction flow in the annular space respectively rose along the wall of the vessel and mixed with each other in the merge tube to continue the reaction, and then entered the releaser. In the eductor, the hydrocarbon product stream was separated from the spent catalyst and then entered into the subsequent diversion system via the oil gas pipeline and further diverted to various products. Each of these products was weighed. The spent catalyst was removed with steam and then introduced into the regenerator where the coke was removed by heating with air. The regenerated catalyst was recycled to the reactor for reuse.
[0070]
The main operating conditions, product distribution and main product characteristics are shown in Table 3, Table 4 and Table 5, respectively. From Table 4 and Table 5, when gasoline is produced as the main target product, the yield of gasoline can reach 59.49% by weight, and the yield of light oil is 78.14% by weight. It can be seen that the total yield of the product can reach 90.00% by weight, and dry gas and coke can be obtained at a lower yield, resulting in a good gasoline product.
[0071]
Example 4
This example shows the test results obtained when diesel oil was produced as the main target product using the process provided in the present invention.
[0072]
The main steps of the test are as follows: As shown in FIG. 7, the raw materials shown in Table 1 are mixed with the recirculated oil of this unit, and the mixed oil is heated in a preheating furnace and supplied to the inner pipe of the double pipe upflow reactor. The mixed catalyst from the catalyst mixing vessel 16 where the regenerated catalyst and spent catalyst are mixed is contacted. Coke diesel oil (density 0.8520g / cm ^Three , Sulfur content 8225 ppm, nitrogen content 5018 ppm, and cetane number 47) were fed into the annular space between the inner and outer tubes and contacted with the mixed catalyst. The reaction flow in the inner tube and the reaction flow in the annular space respectively rose along the wall of the vessel and then mixed with each other in the confluence tube and continued to react and entered the freezer. Within the eductor, the hydrocarbon product stream was separated from the spent catalyst and then entered the subsequent diversion system via the oil gas pipeline and further diverted to various products. Each of these products was weighed. The spent catalyst is removed with steam, and then a part of the removed catalyst is introduced into the regenerator, the coke is heated and removed with air, and the remainder of the spent catalyst is fed directly to the catalyst mixing vessel 16. Mixed with regenerated catalyst. At this time, the mixing ratio of the regenerated catalyst to the used catalyst was set to 2: 1. The mixed catalyst was then recycled to the reactor for reuse.
[0073]
The main operating conditions, product distribution and main product characteristics are shown in Table 3, Table 4 and Table 5, respectively. From Tables 4 and 5, when diesel oil is produced as the main target product, the yield of diesel oil can reach 35.13% by weight and the total yield of liquid product is 89.93% by weight. It can be seen that dry gas and coke are obtained in lower yields.
[0074]
Example 5
This example shows the test results obtained when liquefied petroleum gas and diesel oil were produced as main target products using the process provided in the present invention.
[0075]
The main steps of the test are as follows: The raw materials shown in Table 1 are mixed with the recirculated oil from this unit, and the mixed oil is heated in the preheating furnace and then supplied to the inner pipe of the double pipe upflow reactor, and flows from the regenerator and Contacted with the regenerated catalyst pulled up with a pre-pumping medium. The gasoline fraction produced in this unit was supplied to the annular space between the inner and outer tubes and contacted with the regenerated catalyst. The reaction flow in the inner tube and the reaction flow in the annular space respectively rose along the wall of the vessel, mixed with each other in the merge tube and continued to react, and then entered the releaser. Within the eductor, the hydrocarbon product stream was separated from the spent catalyst and entered the subsequent diversion system via the oil gas pipeline and further diverted to various products. Each of these products was weighed. The spent catalyst was removed with steam and then introduced into the regenerator where the coke was removed by heating with air. The regenerated catalyst was recycled to the reactor for reuse.
[0076]
The main operating conditions, product distribution and main product characteristics are shown in Table 3, Table 4 and Table 5, respectively. From Tables 4 and 5, when liquefied petroleum gas and diesel oil are produced as the main target products, the yield of liquefied petroleum gas can reach 19.08% by weight and the yield of diesel oil is 31. It can be seen that the total yield of liquid product can reach 88.80% by weight, with dry gas and coke being obtained in lower yields.
[0077]
In the following examples, the relay disassembly process is further illustrated, but not limited thereto. The catalyst used in the following examples is a commercial product manufactured by QiLu Petrochemical Catalyst Factory in China, under the trademarks RMG, CIP-1 and CEP respectively. These three types of catalysts were treated with hot water over time, and their main characteristics are shown in Table 6. The hydrocarbon raw material used in each example is DaQing VGO mixed with 30% by weight of VR, and the characteristics are shown in Table 1. The test equipment used in the following examples was a double tube upflow reactor employing a pilot FCC unit.
[0078]
Example 6
This example shows that liquefied petroleum gas, gasoline and diesel oil can be obtained in higher yields using heavy petroleum hydrocarbons as feedstock and using the relay cracking process provided in the present invention.
[0079]
The main steps of the test are as follows: As shown in FIG. 10, the regenerated catalyst was introduced into the bottom of the double-pipe upflow reactor via the catalyst inlet conduit 1 and flowed upward by the action of pre-pumping steam. 70% by weight of the catalyst flows into the inner pipe 2, and the remaining 30% by weight of the catalyst enters the annular space between the inner pipe 2 and the outer pipe 3 and continues to flow upward by the action of the preliminary pulling steam. It was. The hydrocarbon feedstock shown in Table 1 was preheated, supplied to the inner pipe via the nozzle 8, and contacted with the catalyst. The reaction stream continued to flow upward along the vessel wall. The mixture of the reaction oil gas and the catalyst from the inner pipe merges with the regenerated catalyst stream from the annular space between the inner pipe 2 and the outer pipe 3 in the merge pipe 4, and the mixed stream is the merge pipe and high-speed gas. / Through the solids separator into the freer 12 where the hydrocarbon product stream was separated from the spent catalyst. The separated hydrocarbon product stream entered the subsequent separation system 14 and was further separated into various products. The spent catalyst fell into the remover 13, where the reaction oil gas joined by the catalyst was removed by the action of steam, the removed catalyst was introduced into the regenerator 15, and the coke was heated and removed with air. The regenerated catalyst was recycled to the regenerator for reuse.
[0080]
The main operating conditions and product distribution are shown in Table 7. From Table 7, according to the present invention, the total liquid yield of light hydrocarbons (liquefied petroleum gas + gasoline + diesel oil) is 86.62% by weight, and dry gas and coke are obtained at a lower yield. I understand that
[0081]
Example 7
This example shows that light olefins such as propylene can be obtained in higher yields by using the relay cracking process of the present invention when heavy petroleum hydrocarbons are used as feedstock.
[0082]
The main steps of the test are as follows: As shown in FIG. 11, the regenerated catalyst is connected to the inner pipe 35 of the double pipe upflow reactor having two pipes for supplying the catalyst via the catalyst inlet pipes 21 and 22, and the inner pipe 35 and the outer pipe. 36, respectively, both of which flowed upward due to the action of the pre-drawing medium. The catalyst supplied to the inner pipe was 40% by weight of the total weight of the catalyst, and the catalyst supplied to the annular space was 60% by weight of the total weight of the catalyst. The hydrocarbon feed was fed through the nozzle 32 into the reactor inner tube and contacted with the catalyst, and the reaction stream flowed upward along the vessel wall. The reaction stream from the inner pipe merges with the regenerated catalyst stream from the annular space between the inner pipe 35 and the outer pipe 36 in the merge pipe 38, after which the mixed stream passes through the merge pipe and the high-speed gas / solid separator. Through the releaser 12. In the releaser, the hydrocarbon product stream was separated from the spent catalyst. The separated hydrocarbon product stream entered the subsequent separation system 14 and was further separated into various products. The spent catalyst fell into the remover 13, where the reaction oil gas joined by the catalyst was removed by the action of steam. The removed catalyst was introduced into the regenerator 15, and the coke was removed by heating with air. The regenerated catalyst was recycled to the reactor for reuse.
[0083]
The main operating conditions and product distribution are shown in Table 7. From Table 7, the yields of ethylene, propylene and butylene can reach 4.79%, 24.01% and 15.28%, respectively, when light olefins mainly composed of propylene are produced as the main target product. It can be seen that dry gas and coke can be obtained at lower yields.
[0084]
Example 8
This example shows that light olefins such as ethylene can be obtained in higher yields by using the relay cracking process of the present invention starting from heavy petroleum hydrocarbons.
[0085]
The main steps of the test are as follows: As shown in FIG. 11, the regenerated catalyst enters the double pipe upflow reactor inner tube 35 having two conduits for catalyst supply and the annular space between the inner tube 35 and the outer tube 36. , Respectively, via catalyst inlet conduits 21 and 22, both of which flowed upwards due to the action of the pre-drawing medium. The catalyst supplied to the inner tube was 50% of the total weight of the catalyst, and the catalyst supplied to the annular space was also 50% of the total weight of the catalyst. The hydrocarbon feed was fed through the nozzle 32 into the reactor inner tube and contacted with the catalyst, and the reaction stream flowed upward along the vessel wall. The reaction flow from the inner tube merges with the regenerated catalyst flow from the annular space between the inner tube 35 and the outer tube 36 at the merge tube inlet 38, and then through the merge tube and the high-speed gas / solid separator. The releaser 12 was entered. In the releaser, the hydrocarbon product stream was separated from the spent catalyst. The separated hydrocarbon product stream entered the subsequent separation system 14 and was further separated into various products. The spent catalyst fell into the remover 13, where the reaction oil gas joined by the catalyst was removed by the action of steam. The removed catalyst was introduced into the regenerator 15, and the coke was removed by heating with air. The regenerated catalyst was recycled to the reactor for reuse.
[0086]
The main operating conditions and product distribution are shown in Table 7. Table 7 shows that when the process of the present invention is used to produce light olefins consisting primarily of ethylene as the main target product, the yields of ethylene, propylene, and butylene are 27.63%, 17.62%, and It can be seen that it can reach 5.06%.
[0087]
Comparative example
In the comparative example, a conventional upflow reactor was used and the same raw materials, catalyst and operating conditions as those used in Example 6 were used.
[0088]
The main steps of the test are as follows. The preheated feed was fed to the upflow reactor and contacted with the regenerated catalyst that entered from the regenerator and was lifted with a pre-pumping medium. The reaction stream formed entered the release through a riser, in which the hydrocarbon product stream was separated from the spent catalyst. The separated hydrocarbon product stream then entered the subsequent diversion system via an oil gas pipeline and was further diverted to various products. Each of these products was weighed. The spent catalyst was removed with steam and then introduced into the regenerator where the coke was removed by heating with air. The regenerated catalyst was recycled to the reactor for reuse.
[0089]
The main operating conditions and product distribution are shown in Table 7. By comparing Example 6 with this comparative example, it can be seen that the process of the present invention has a relatively strong heavy oil conversion capacity and the desired product selectivity.
[0090]
[Table 1]

[0091]
[Table 2]

[0092]
[Table 3]

[0093]
[Table 4]

[0094]
[Table 5]

[0095]
[Table 6]

[0096]
[Table 7]

[Brief description of the drawings]
FIG. 1 is a schematic structural diagram of a double tube upflow reactor having a single conduit for feeding catalyst.
FIG. 2 is a schematic structural diagram of a junction region of an inner tube, an outer tube, and a merging tube in a double tube upflow reactor having a single conduit for supplying a catalyst.
FIG. 3 is a schematic view of a set mode of inner and outer tube feed nozzles in a double tube upflow reactor having a single conduit for feeding catalyst.
FIG. 4 is a schematic structural diagram of a double tube upflow reactor having two conduits for supplying catalyst.
FIG. 5 is a schematic structural diagram of a junction region of an inner tube, an outer tube, and a merged tube in a double tube upflow reactor having two conduits for supplying a catalyst.
FIG. 6 is a main flow diagram of a catalytic cracking process of petroleum hydrocarbons using a double pipe upflow reactor.
FIG. 7 is a main flow diagram of a catalytic cracking process of petroleum hydrocarbons using a double pipe upflow reactor.
FIG. 8 is a main flowchart of the catalytic cracking treatment of petroleum hydrocarbons using a double pipe upflow reactor.
FIG. 9 is a main flow diagram of a catalytic cracking process of petroleum hydrocarbons using a double pipe upflow reactor.
FIG. 10 is a main flowchart of the petroleum hydrocarbon relay cracking process.
FIG. 11 is a main flowchart of a petroleum hydrocarbon relay cracking process.
[Explanation of symbols]
1 catalyst inlet conduit, 2 inner tube, 3 outer tube, 5, 6, 7 preliminary pulling distribution ring, 8, 9 supply nozzle, 10 fixing member.

Claims (9)

(1) supplying the catalyst flowing upward under the action of the preliminary pulling medium from the catalyst inlet conduit into the inner tube of the double tube upflow reactor and the annular space between the inner tube and the outer tube; ,
(2) A hydrocarbon raw material is supplied to the inner tube of the reactor and the annular space between the inner tube and the outer tube, and the hydrocarbon raw material comes into contact with the inner tube and the catalyst in the annular space. By forming a mixture of oil and catalyst, the reaction of the hydrocarbon raw material is performed under catalytic cracking reaction conditions so that the reaction flow containing the reaction oil gas and the catalyst flows upward along the wall of the vessel. And steps to
(3) The reaction flows from both the inner pipe and the annular space between the inner pipe and the outer pipe merge at the inlet of the merge pipe, and this mixed stream enters the separation device via the merge pipe, and this separation Separating the hydrocarbon conversion product from the spent catalyst in the apparatus;
(4) further separating the hydrocarbon conversion product into various products including gasoline, diesel oil and liquefied gas, removing and regenerating spent catalyst, and reusing the regenerated catalyst; Recycling the hydrocarbon into a reactor, comprising the steps of:
The hydrocarbon raw material supplied to the inner pipe is straight-run gas oil, coke gas oil, deasphalted oil, hydrofound oil, hydrocracked tail oil, vacuum gas oil, vacuum residue, atmospheric residue and those Selected from the group consisting of mixtures,
Petroleum carbonization, wherein the hydrocarbon feed supplied to the annular space between the inner and outer tubes is selected from the group consisting of gaseous hydrocarbons, refinery gas, gasoline fractions, diesel oil fractions and mixtures thereof Hydrogen catalytic cracking process.   The processing method according to claim 1, wherein the double tube upflow reactor comprises a plurality of pre-pull distribution rings. In the inner pipe, the reaction of the hydrocarbon raw material is performed at a reaction temperature of 460 to 580 ° C., a reaction pressure of 0.1 to 0.6 MPa, a ratio of catalyst to oil of 3 to 15, and an oil gas residence time of 1.0 to 10 in the inner pipe. Second, under the conditions of a catalyst temperature of 620 to 720 ° C. before contact with the raw material and an atomization vapor amount of 1 to 20% by weight,
In the annular space between the inner tube and the outer tube, the reaction of the hydrocarbon raw material is performed at a reaction temperature of 300 to 680 ° C., a reaction pressure of 0.1 to 0.6 MPa, a ratio of catalyst to oil of 2 to 30, oil gas retention The processing method according to claim 1, wherein the treatment is performed under the conditions of a time of 0.5 to 20 seconds and an atomization vapor amount of 1 to 20% by weight. In the inner pipe, the reaction of the hydrocarbon raw material has a reaction temperature of 480 to 550 ° C., a reaction pressure of 0.2 to 0.4 MPa, a ratio of catalyst to oil of 4 to 10, and an oil gas residence time of 1.5 to 5 in the inner pipe. 0.0 second, under conditions of a catalyst temperature of 650 to 700 ° C. before contact with the raw material and an atomization vapor amount of 2 to 15% by weight,
In the annular space between the inner pipe and the outer pipe, the reaction of the hydrocarbon raw material is performed at a reaction temperature of 400 to 600 ° C., a reaction pressure of 0.2 to 0.4 MPa, a ratio of catalyst to oil of 4 to 20, and oil gas retention. The processing method according to claim 1, wherein the treatment is performed under conditions of a time of 1 to 15 seconds and an atomization vapor amount of 1 to 15 wt%.   The catalyst supplied to the inner pipe of the double pipe upflow reactor and the annular space between the inner pipe and the outer pipe is a regenerated catalyst, a semi-regenerated catalyst, a spent catalyst and a mixture thereof. The carbon content of the catalyst selected from the group consisting of and supplied to the inner tube may be different from the carbon content of the catalyst supplied to the annular space between the inner tube and the outer tube. Processing method.   The double-pipe upflow reactor has a single conduit for supplying catalyst, a catalyst inlet conduit (1), an inner tube (2), an outer tube (3), and a junction tube. It mainly includes members of (4), preliminary pulling distribution rings (5), (6) and (7), and supply nozzles (8) and (9), and an inner pipe (2) and an outer pipe (3). Is coaxial, the ratio of the cross-sectional area of the inner pipe to the cross-sectional area of the annular space between the inner pipe and the outer pipe is 1: 0.1 to 10, and the lower end of the inner pipe (2) is the catalyst inlet The inner pipe is 10 to 70% of the total length of the reactor, one end of the junction pipe (4) is connected to the upper end of the outer pipe (3), and the other end is Connected to the gas / solid separator, the ratio of the cross-sectional area of the confluence pipe (4) and the inner pipe (2) is 1: 0.2 to 0.8, and the preliminary pulling distribution ring (5), (6) and 7) Each reactor is positioned at the bottom of the inner and outer tubes, the processing method according to claim 1. The ratio of the cross-sectional area of the inner pipe in the double pipe upflow reactor to the cross-sectional area of the annular space between the inner pipe and the outer pipe is 1: 0.2-2;
The length of the inner pipe of the double pipe upflow reactor is 20-60% of the total length of the reactor;
The distance from the outlet end of the inner pipe of the double pipe upflow reactor to the outlet end of the merged pipe is 1 to 30 meters,
The processing method according to claim 6, wherein 2 to 12 presser wires or tension bars are installed between an inner tube and an outer tube of the double pipe upflow reactor.   The double pipe upflow reactor has two conduits for supplying catalyst, catalyst inlet conduits (21) and (22), an inner tube (35), an outer tube (36), It mainly includes members of a confluence pipe (38), pre-lift distribution rings (31) and (33), and supply nozzles (32) and (34), and an inner pipe (35) and an outer pipe (36) are coaxial. The ratio of the cross-sectional area of the inner tube to the cross-sectional area of the annular space between the inner tube and the outer tube is 1: 0.1 to 10, and the catalyst inlet conduit (21) is the inner tube (35). The length of the inner tube is 10 to 70% of the total length of the reactor, and the distance from the lower end of the outer tube (36) to the lower end of the inner tube (35) is 2 of the total length of the reactor. ~ 20%, the catalyst inlet conduit (22) is connected to the lower end of the outer pipe (36), and one end of the confluence pipe (38) is above the outer pipe (36). The other end is connected to the gas / solid separator, the ratio of the cross-sectional area of the merge pipe (38) and the inner pipe (35) is 1: 0.2 to 0.8, (31) and (33) are positioned at the bottom of the inner tube and the bottom of the annular space between the inner tube and the outer tube, respectively, and the supply nozzles (32) and (34) are respectively below the inner tube and the outer tube. The processing method according to claim 1, wherein the processing method is positioned on a portion. The ratio of the cross-sectional area of the inner pipe to the cross-sectional area of the annular space between the inner pipe and the outer pipe is 1: 0.1-2 in the double pipe upflow reactor,
The double pipe upflow reactor has an inner pipe that is 15-50% of the total length of the upflow reactor;
The distance from the lower end of the outer pipe to the lower end of the inner pipe in the double pipe upflow reactor is 5 to 15% of the total length of the upflow reactor,
The ratio of the cross-sectional area of the combined pipe and the inner pipe is 1: 0.3 to 0.7 in the double pipe upflow reactor,
2 to 12 presser wires or tension bars are installed between the inner tube and the outer tube of the double tube upflow reactor,
The processing method according to claim 8, wherein the distance from the outlet end of the inner pipe of the double pipe upflow reactor to the outlet end of the merged pipe is 0.5 to 20 meters.

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