CN102875283A - Method for preparing low-carbon olefins by using methanol and naphtha - Google Patents

Method for preparing low-carbon olefins by using methanol and naphtha Download PDF

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CN102875283A
CN102875283A CN201110193465XA CN201110193465A CN102875283A CN 102875283 A CN102875283 A CN 102875283A CN 201110193465X A CN201110193465X A CN 201110193465XA CN 201110193465 A CN201110193465 A CN 201110193465A CN 102875283 A CN102875283 A CN 102875283A
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reaction
enter
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catalyzer
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CN102875283B (en
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齐国祯
钟思青
李晓红
王洪涛
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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

Abstract

The invention relates to a method for preparing low-carbon olefins by using methanol and naphtha, mainly solving the problem of low yield of low-carbon olefins in the prior art. The method disclosed herein mainly comprises the following steps: (1) letting a raw material containing naphtha enter into a first reaction zone, and letting the product flow and catalyst enter into a disengager; letting the a raw material containing methanol enter into a second reaction zone, and letting the product flow and catalyst enter into a third reaction zone, and letting the generated product flow and catalyst enter into the disengager; (2) letting the gas-phase flow in the disengager enter into a separation section to separate a product containing low-carbon olefins and C4-C8 mixed hydrocarbons, wherein letting the flow of the C4-C8 mixed hydrocarbons enter into a fourth reaction zone, and letting the product flow and catalyst enter into the third reaction zone; and (3) letting the catalyst in the disengager enter into the regenerator, dividing the generated catalyst into three parts, letting one part enter into the first reaction zone, letting one part enter into the second reaction zone, and letting the rest part enter into the fourth reaction zone. The method disclosed herein well solves the problem and can be used in the industrial production of low-carbon olefins.

Description

The method that is prepared low-carbon alkene by methyl alcohol and petroleum naphtha
Technical field
The present invention relates to a kind of method that is prepared low-carbon alkene by methyl alcohol and petroleum naphtha.
Technical background
Low-carbon alkene, namely ethene and propylene are two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are to produce by petroleum path, but because limited supply and the higher price of petroleum resources, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people begin to greatly develop the technology that alternative materials transforms ethene processed, propylene.Wherein, the important alternative materials that is used for light olefin production of one class is oxygenatedchemicals, such as alcohols (methyl alcohol, ethanol), ethers (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed by coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, such as methyl alcohol, can be made by coal or Sweet natural gas, and technique is very ripe, can realize up to a million tonnes industrial scale.Because the popularity in oxygenatedchemicals source, add and transform the economy that generates light olefin technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), particularly the technique by preparing olefin by conversion of methanol (MTO) is subject to increasing attention.
Petroleum naphtha is a kind of light-end products, is cut corresponding cut and is got by crude distillation or oil secondary processing.Its boiling spread is decided according to need, is generally wider boiling range, such as 20-220 ℃.Petroleum naphtha is the pyrolysis in tubular furnace preparing ethylene, and propylene and catalytic reforming are produced the important source material of benzene,toluene,xylene.As cracking stock, require petroleum naphtha form in the content of alkane and naphthenic hydrocarbon be not less than 70% (volume).The naphtha catalytic pyrolysis preparing low-carbon alkene then is under the condition that catalyzer exists, and petroleum hydrocarbon is carried out the production process that cracking obtains low-carbon alkene.Compare with traditional tube furnace steam heat cracking, this process reaction temperature is than low 50～200 ℃ approximately of steam cracking reactions, and energy consumption significantly reduces; Cracking furnace pipe inwall coking rate also can reduce, thereby but prolong operation cycle increases the boiler tube life-span; Simultaneously Carbon emission also can reduce, and has alleviated pollution, and can adjust the product mix flexibly.
Technology and reactor that a kind of oxygenate conversion is low-carbon alkene have been announced among the US6166282, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu reaction of gas speed is finished, after rising to the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Because reaction after product gas and catalyzer sharp separation have effectively prevented the generation of secondary reaction.Through analog calculation, to compare with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyzer all greatly reduce.
The multiple riser reaction unit of having announced among the CN1723262 with central catalyst return is low-carbon alkene technique for oxygenate conversion, this covering device comprises a plurality of riser reactors, gas solid separation district, a plurality of offset components etc., each riser reactor has the port of injecting catalyst separately, be pooled to the disengaging zone of setting, catalyzer and gas product are separated.But there is the lower shortcoming of yield of light olefins in the method.
Announced a kind of method of methanol production propylene among EP0448000 and the EP0882692, methyl alcohol at first is converted into DME and water, then mixture is transported to the First reactor, and adds steam in this reactor.In the first reactor methyl alcohol with (or) dme or its mixture contact with catalyzer and react, catalyzer adopts the special-purpose ZSM-5 catalyzer that contains ZnO and CdO, 280～570 ℃ of temperature of reaction, pressure 0.01～0.1MPa prepares the product take propylene as main hydro carbons.Heavier product such as C 5 +The hydrocarbon continuation is reacted in second reactor and is converted into take propylene as main hydro carbons, sends separator back to after cooling.Product is compressed, can obtain purity after further refining is 97% chemical grade propylene.But adopt a plurality of fixed-bed reactor in this technique, because the restriction of the activity of catalyzer therefore need frequent blocked operation, and the heat-obtaining problem is also very complicated.
US 20070083071 has announced the processing method that a kind of hydrocarbon catalytic pyrolysis is produced ethene, propylene, hydrocarbon feed is converted into the product that comprises low-carbon alkene in catalytic cracker, then product stream is separated into C2～C3 alkane, C2～C3 alkene, three kinds of logistics of C4+ hydrocarbon by series of process, C2～C3 alkane is returned tube cracking furnace carry out thermo-cracking, the C4+ hydrocarbon returns catalytic cracker and carries out catalytic pyrolysis, finally obtains ethene, the propylene product of higher yields.The method adopts riser reactor, and reactant residence time is shorter, and low-carbon alkene product once through yield is lower.
Since the reaction of naphtha catalytic cracking and preparing olefin by conversion of methanol the purpose product---low-carbon alkene is identical, and the main ingredient kind in the product is roughly the same separately, the catalyst system that adopts is also roughly the same, and from the reaction mechanism angle, all have the process that is cracked into the small molecules hydro carbons by macromole hydrocarbon or intermediate, so these two kinds of Technologies are had ready conditions and are coupled.The present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the not high problem of yield of light olefins that exists in the prior art, and a kind of new method that is prepared low-carbon alkene by methyl alcohol and petroleum naphtha is provided.The method is used for the production of low-carbon alkene, has the higher advantage of yield of light olefins.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of method that is prepared low-carbon alkene by methyl alcohol and petroleum naphtha, mainly may further comprise the steps: at least one position of at least one opening for feed that the raw material that (1) comprises petroleum naphtha separates from the first reaction zone bottom or along the first reaction zone axial direction due enters the first reaction zone, and product stream and the catalyzer of generation enter settling vessel; The raw material that comprises methyl alcohol enters second reaction zone, and the product stream of generation and catalyzer enter the 3rd reaction zone, and product stream and catalyzer that the 3rd reaction zone generates enter settling vessel; (2) enter centrifugal station after gaseous stream and the catalyst separating in the settling vessel, isolate the product that comprises low-carbon alkene, C4～C8 hydrocarbon mixture, logistics comprising C4～C8 hydrocarbon mixture enters the 4th reaction zone, and the product stream of generation and catalyzer enter the 3rd reaction zone; (3) catalyzer enters revivifier regeneration in the settling vessel behind stripping, and the catalyzer after the regeneration is divided into three parts, and a part enters the first reaction zone, and a part enters second reaction zone, and a part enters the 4th reaction zone.
In the technique scheme, described catalyzer comprises ZSM-5 molecular sieve, SiO 2/ Al 2O 3Mol ratio is 10～100; Catalyzer coke content massfraction after the described regeneration is 0.01～0.5%; Also comprise water vapour in described the first reaction zone feeds, the weight ratio of water vapour and petroleum naphtha is 0.05～1.5: 1; Be mainly methyl alcohol in the 3rd reaction zone feeds; Described petroleum naphtha boiling range is between 20 ℃～220 ℃; Reaction conditions is in described the first reaction zone: temperature of reaction is 570～670 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 4～10 meter per seconds; Reaction conditions is in the second reaction zone: temperature of reaction is 480～600 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 4～10 meter per seconds; Reaction conditions is in the 3rd reaction zone: temperature of reaction is 480～600 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 1～3 meter per second; Reaction conditions is in the 4th reaction zone: temperature of reaction is 530～630 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 4～10 meter per seconds; The logistics of the described C4 of comprising～C8 hydrocarbon mixture enters the 4th reaction zone from the 4th reaction zone bottom or from least one opening for feed that in axial direction separates; Catalyst activity sex index after the described regeneration is greater than 0.8; Described the first reaction zone is riser tube; Second reaction zone is riser tube; The 3rd reaction zone is fast bed; The 4th reaction zone is riser tube; Catalyzer after the described regeneration is divided into three parts, and 20～40% weight enter the first reaction zone, and 20～40% weight enter second reaction zone, and 20～60% weight enter the 4th reaction zone.
The regenerated catalyst activity index is used for embodying the regeneration level of decaying catalyst, take live catalyst as benchmark, the amount that transforms light naphthar with each catalyzer under the rigid condition is carried out relatively, and method of calculation are: regenerated catalyst activity index=(the light naphthar amount that live catalyst transforms under light naphthar amount/certain condition that regenerated catalyst transforms under the certain condition) * 100%.Described certain condition or rigid condition refer to adopt fluidized-bed reactor, temperature of reaction be 600 ℃, reaction pressure take gauge pressure count 0, the gas phase residence time is as 4 seconds reaction conditions.
ZSM-5 molecular sieve of the present invention can adopt method known in the field, such as hydrothermal synthesis method, be prepared, understand the metal that optionally load has dehydrogenation functionality at described molecular sieve catalyst, the metal of dehydrogenation functionality is selected from least a in IB in the periodic table of elements, IIB, VB, VIB, VIIB or the VIII family, and the method for metal load on ZSM-5 molecular sieve of dehydrogenation functionality can be adopted method known in the field, such as pickling process or coprecipitation method.After the ZSM-5 molecular sieve of load dehydrogenation functionality metal prepares, add binding agent, make mixed slurry, adopt spray drying process to carry out drying and moulding, then place stoving oven to carry out roasting the catalyst fines after the moulding, obtain catalyst sample after the cooling.Binding agent can be selected SiO 2, Al 2O 3Deng.
Adopt method of the present invention, four reaction areas is set, it is low-carbon alkene that the first reaction zone is mainly used in naphtha catalytic cracking, second reaction zone is mainly used in transforming methyl alcohol, the 3rd reaction zone is mainly used in transforming the gaseous substance in second reaction zone and the 4th reaction zone, and the 4th reaction zone is mainly used in transforming C4～C8 hydrocarbon mixture by product, and adopts the axial admission mode at the first reaction zone, the 4th reaction zone, reduce the raw material dividing potential drop, in the hope of improving the low-carbon alkene transformation efficiency.Settling vessel and revivifier can be arranged apart or the public settling vessel of first, second, third, fourth reaction zone can coaxially be set among the present invention.The 4th reaction zone provides reactant and catalyzer for the 3rd reaction zone, and playing simultaneously is the purpose of the 3rd reaction zone cooling.Therefore, adopt method of the present invention, not only realize energy-optimisedly, and methyl alcohol and petroleum naphtha are transformed the preparation low-carbon alkene be coupled, transform simultaneously the high-carbon hydrocarbon by product that falls to generate, reached the purpose that improves selectivity of light olefin.
Adopt technical scheme of the present invention: described catalyzer comprises ZSM-5 molecular sieve, SiO 2/ Al 2O 3Mol ratio is 10～100; Catalyzer coke content massfraction after the described regeneration is 0.01～0.5%; Also comprise water vapour in described the first reaction zone feeds, the weight ratio of water vapour and petroleum naphtha is 0.05～1.5: 1; Be mainly methyl alcohol in the 3rd reaction zone feeds; Described petroleum naphtha boiling range is between 20 ℃～220 ℃; Reaction conditions is in described the first reaction zone: temperature of reaction is 570～670 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 4～10 meter per seconds; Reaction conditions is in the second reaction zone: temperature of reaction is 480～600 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 4～10 meter per seconds; Reaction conditions is in the 3rd reaction zone: temperature of reaction is 480～600 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 1～3 meter per second; Reaction conditions is in the 4th reaction zone: temperature of reaction is 530～630 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 4～10 meter per seconds; The logistics of the described C4 of comprising～C8 hydrocarbon mixture enters the 4th reaction zone from the 4th reaction zone bottom or from least one opening for feed that in axial direction separates; Catalyst activity sex index after the described regeneration is greater than 0.8; Described the first reaction zone is riser tube; Second reaction zone is riser tube; The 3rd reaction zone is fast bed; The 4th reaction zone is riser tube; Catalyzer after the described regeneration is divided into three parts, 20～40% weight enter the first reaction zone, and 20～40% weight enter second reaction zone, and 20～60% weight enter the 4th reaction zone, the low-carbon alkene carbon base absorption rate can reach 65.06% weight, has obtained preferably technique effect.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for the invention.
Among Fig. 1,1 is the regenerating medium source line; 2 is plug valve to be generated; 3 is revivifier; 4 is buffer zone; 5 is regenerator sloped tube delivering vapor entrance; 6 is the second reaction zone charging; 7 is the 4th reaction zone feeds; 8 is buffer zone; 9 is the first reaction zone and the 4th reaction zone side feed opening; 10 is second reaction zone; 11 is regeneration standpipe; 12 is the 3rd reaction zone; 13 is stripping medium inlet pipeline; 14 is that the outlet of the first reaction zone is slightly revolved; 15 is gas-solid cyclone separator; 16 is exhanst gas outlet; 17 is settling vessel; 18 is stripper; 19 is the first reaction zone; 20 is that the outlet of the 3rd reaction zone is slightly revolved; 21 is the first reaction zone feeds; 22 is the products export pipeline; 23 is the 4th reaction zone; 24 is the 3rd reaction zone feeds; 25 is gas-solid cyclone separator; 26 is regenerator sloped tube; 27 is regenerator sloped tube; 28 is regenerator sloped tube; 29 is buffer zone.
At least one position of at least one opening for feed 9 that the raw material that comprises petroleum naphtha separates from the first reaction zone 19 bottoms or along the first reaction zone axial direction due enters the first reaction zone 19, and the product stream of generation and catalyzer enter settling vessel 17; The raw material that comprises methyl alcohol enters second reaction zone 10, the product stream and the catalyzer that generate enter the 3rd reaction zone 12, product stream and catalyzer that the 3rd reaction zone 12 generates enter settling vessel 17, enter centrifugal station after gaseous stream and the catalyst separating in the settling vessel 17, isolate and comprise low-carbon alkene, the product of C4～C8 hydrocarbon mixture, logistics comprising C4～C8 hydrocarbon mixture enters the 4th reaction zone 23, the product stream and the catalyzer that generate enter the 3rd reaction zone 12, catalyzer enters revivifier 3 regeneration in the settling vessel 17 behind stripping, catalyzer after the regeneration is divided into three parts, a part enters the first reaction zone 19, a part enters second reaction zone 10, and a part enters the 4th reaction zone 23.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
In reaction unit as shown in Figure 1, catalyzer is ZSM-5, SiO 2/ Al 2O 3Mol ratio is 100, loaded Cu/Zn/Co, and the percentage ratio that the loaded metal quality accounts for catalyst quality is Cu:5.53; Zn:2.76; Co:1.68.The raw material that comprises petroleum naphtha enters the first reaction zone from the first reaction zone bottom, and product stream and the catalyzer of generation enter settling vessel; The raw material of methyl alcohol enters second reaction zone, the product stream and the catalyzer that generate enter the 3rd reaction zone, product stream and catalyzer that the 3rd reaction zone generates enter settling vessel, enter centrifugal station after gaseous stream and the catalyst separating in the settling vessel, isolate and comprise low-carbon alkene, the product of C4～C8 hydrocarbon mixture, wherein the logistics of C4～C8 hydrocarbon mixture enters the 4th reaction zone, the product stream and the catalyzer that generate enter the 3rd reaction zone, catalyzer enters revivifier regeneration in the settling vessel behind stripping, catalyzer after the regeneration is divided into three parts, 20% weight enters the first reaction zone, and 20% weight enters second reaction zone, and 60% weight enters the 4th reaction zone.The first reaction zone is riser tube; Second reaction zone is riser tube; The 3rd reaction zone is fast bed; The 4th reaction zone is riser tube.Catalyzer coke content massfraction after the regeneration is to comprise also in 0.01%, the first reaction zone feeds that water vapour, the weight ratio of water vapour and petroleum naphtha are 1.5: 1, is methyl alcohol in the 3rd reaction zone feeds, and the petroleum naphtha composition sees Table 1.Reaction conditions is in the first reaction zone: temperature of reaction is 570 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 4 meter per seconds; Reaction conditions is in the second reaction zone: temperature of reaction is 480 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 4 meter per seconds; Reaction conditions is in the 3rd reaction zone: temperature of reaction is 482 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 1 meter per second; Reaction conditions is in the 4th reaction zone: temperature of reaction is 530 ℃, and reaction pressure is counted 0.01～MPa with gauge pressure, and the gas phase linear speed is 4 meter per seconds.The logistics of C4～C8 hydrocarbon mixture enters the 4th reaction zone from the 4th reaction zone bottom.Catalyst activity sex index after the regeneration is 0.93.Methyl alcohol and naphtha feed weight ratio are 1: 1.Keep the stability of catalyst flow control, gas product adopts online gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate is 59.28% weight.
[embodiment 2]
According to embodiment 1 described condition and step, catalyzer is ZSM-5, SiO 2/ Al 2O 3Mol ratio is 10, comprises that the raw material of petroleum naphtha enters the first reaction zone from the first reaction zone bottom with along an opening for feed on the first reaction zone axial direction due, and this opening for feed distance the first reaction zone bottom is 1/2 first reaction zone height.Catalyzer after the regeneration is divided into three parts, and 40% weight enters the first reaction zone, and 40% weight enters second reaction zone, and 20% weight enters the 4th reaction zone.Catalyzer coke content massfraction after the regeneration is to comprise also in 0.5%, the first reaction zone feeds that water vapour, the weight ratio of water vapour and petroleum naphtha are 0.05: 1.Reaction conditions is in the first reaction zone: temperature of reaction is 670 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 10 meter per seconds; Reaction conditions is in the second reaction zone: temperature of reaction is 600 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 10 meter per seconds; Reaction conditions is in the 3rd reaction zone: temperature of reaction is 600 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 3 meter per seconds; Reaction conditions is in the 4th reaction zone: temperature of reaction is 630 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 10 meter per seconds.The logistics of C4～C8 hydrocarbon mixture enters the 4th reaction zone from the 4th reaction zone bottom with from an opening for feed of in axial direction going up, and this opening for feed distance the 4th reaction zone bottom is 1/2 the 4th reaction zone height.Catalyst activity sex index after the regeneration is 0.8.Keep the stability of catalyst flow control, gas product adopts online gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate is 62.49% weight.
[embodiment 3]
According to embodiment 1 described condition and step, catalyzer is ZSM-5, SiO 2/ Al 2O 3Mol ratio is 70, comprises that the raw material of petroleum naphtha enters the first reaction zone from the first reaction zone bottom with along two opening for feeds on the first reaction zone axial direction due, and two opening for feed distance the first reaction zone bottoms are respectively 1/3,1/2 first reaction zone height.Catalyzer after the regeneration is divided into three parts, and 30% weight enters the first reaction zone, and 30% weight enters second reaction zone, and 40% weight enters the 4th reaction zone.Catalyzer coke content massfraction after the regeneration is to comprise also in 0.05%, the first reaction zone feeds that water vapour, the weight ratio of water vapour and petroleum naphtha are 0.5: 1.Reaction conditions is in the first reaction zone: temperature of reaction is 650 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 7 meter per seconds; Reaction conditions is in the second reaction zone: temperature of reaction is 560 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 6 meter per seconds; Reaction conditions is in the 3rd reaction zone: temperature of reaction is 550 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 6.3 meter per seconds; Reaction conditions is in the 4th reaction zone: temperature of reaction is 610 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 7 meter per seconds.The logistics of C4～C8 hydrocarbon mixture enters the 4th reaction zone from the 4th reaction zone bottom with from two opening for feeds in axial direction going up, and two opening for feed distance the 4th reaction zone bottoms are respectively 1/3,1/2 the 4th reaction zone height.Catalyst activity sex index after the regeneration is 0.94.Keep the stability of catalyst flow control, gas product adopts online gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate is 65.06% weight.
[embodiment 4]
According to embodiment 1 described condition and step, catalyzer is ZSM-5, SiO 2/ Al 2O 3Mol ratio is 30, comprises that the raw material of petroleum naphtha enters the first reaction zone from the first reaction zone bottom with along three opening for feeds on the first reaction zone axial direction due, and three opening for feed distance the first reaction zone bottoms are respectively 1/4,1/3,1/2 first reaction zone height.Catalyzer after the regeneration is divided into three parts, and 33% weight enters the first reaction zone, and 40% weight enters second reaction zone, and 27% weight enters the 4th reaction zone.Catalyzer coke content massfraction after the regeneration is to comprise also in 0.1%, the first reaction zone feeds that water vapour, the weight ratio of water vapour and petroleum naphtha are 0.25: 1.Reaction conditions is in the first reaction zone: temperature of reaction is 660 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and the gas phase linear speed is 5 meter per seconds; Reaction conditions is in the second reaction zone: temperature of reaction is 570 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and the gas phase linear speed is 5 meter per seconds; Reaction conditions is in the 3rd reaction zone: temperature of reaction is 560 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and the gas phase linear speed is 4.8 meter per seconds; Reaction conditions is in the 4th reaction zone: temperature of reaction is 615 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and the gas phase linear speed is 4 meter per seconds.The logistics of C4～C8 hydrocarbon mixture enters the 4th reaction zone from the 4th reaction zone bottom with from two opening for feeds in axial direction going up, and two opening for feed distance the 4th reaction zone bottoms are respectively 1/3,1/2 the 4th reaction zone height.Catalyst activity sex index after the regeneration is 0.94.Keep the stability of catalyst flow control, gas product adopts online gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate is 60.67% weight.
[comparative example 1]
According to embodiment 1 described condition and step, just the 4th reaction zone is not set, the low-carbon alkene carbon base absorption rate is 52.69% weight.
[comparative example 2]
According to embodiment 1 described condition and step, just the 3rd reaction zone and the 4th reaction zone are not set, the low-carbon alkene carbon base absorption rate is 47.28% weight.
Obviously, adopt method of the present invention, can reach the purpose that improves yield of light olefins, have larger technical superiority, can be used in the industrial production of low-carbon alkene.

Claims (10)

1. one kind prepares the method for low-carbon alkene by methyl alcohol and petroleum naphtha, mainly may further comprise the steps:
(1) at least one position of at least one opening for feed that the raw material that comprises petroleum naphtha separates from the first reaction zone bottom or along the first reaction zone axial direction due enters the first reaction zone, and product stream and the catalyzer of generation enter settling vessel; The raw material that comprises methyl alcohol enters second reaction zone, and the product stream of generation and catalyzer enter the 3rd reaction zone, and product stream and catalyzer that the 3rd reaction zone generates enter settling vessel;
(2) enter centrifugal station after gaseous stream and the catalyst separating in the settling vessel, isolate the product that comprises low-carbon alkene, C4～C8 hydrocarbon mixture, logistics comprising C4～C8 hydrocarbon mixture enters the 4th reaction zone, and the product stream of generation and catalyzer enter the 3rd reaction zone;
(3) catalyzer enters revivifier regeneration in the settling vessel behind stripping, and the catalyzer after the regeneration is divided into three parts, and a part enters the first reaction zone, and a part enters second reaction zone, and a part enters the 4th reaction zone.
2. describedly according to claim 1 prepare the method for low-carbon alkene by methyl alcohol and petroleum naphtha, it is characterized in that described catalyzer comprises ZSM-5 molecular sieve, SiO 2/ Al 2O 3Mol ratio is 10～100.
3. describedly according to claim 1 prepare the method for low-carbon alkene by methyl alcohol and petroleum naphtha, it is characterized in that the catalyzer coke content massfraction after the described regeneration is 0.01～0.5%.
4. describedly according to claim 1 prepare the method for low-carbon alkene by methyl alcohol and petroleum naphtha, it is characterized in that also comprising water vapour in described the first reaction zone feeds that the weight ratio of water vapour and petroleum naphtha is 0.05～1.5: 1; Be mainly methyl alcohol in the 3rd reaction zone feeds.
5. describedly according to claim 1 prepare the method for low-carbon alkene by methyl alcohol and petroleum naphtha, it is characterized in that described petroleum naphtha boiling range is between 20 ℃～220 ℃.
6. the described method that is prepared low-carbon alkene by methyl alcohol and petroleum naphtha according to claim 1, it is characterized in that reaction conditions is in described the first reaction zone: temperature of reaction is 570～670 ℃, reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 4～10 meter per seconds; Reaction conditions is in the second reaction zone: temperature of reaction is 480～600 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 4～10 meter per seconds; Reaction conditions is in the 3rd reaction zone: temperature of reaction is 480～600 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 1～3 meter per second; Reaction conditions is in the 4th reaction zone: temperature of reaction is 530～630 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 4～10 meter per seconds.
7. describedly according to claim 1 prepare the method for low-carbon alkene by methyl alcohol and petroleum naphtha, it is characterized in that the logistics of the described C4 of comprising～C8 hydrocarbon mixture enters the 4th reaction zone from the 4th reaction zone bottom or from least one opening for feed that in axial direction separates.
8. describedly according to claim 1 prepare the method for low-carbon alkene by methyl alcohol and petroleum naphtha, it is characterized in that catalyst activity sex index after the described regeneration is greater than 0.8.
9. describedly according to claim 1 prepare the method for low-carbon alkene by methyl alcohol and petroleum naphtha, it is characterized in that described the first reaction zone is riser tube; Second reaction zone is riser tube; The 3rd reaction zone is fast bed; The 4th reaction zone is riser tube.
10. the described method that is prepared low-carbon alkene by methyl alcohol and petroleum naphtha according to claim 1, it is characterized in that the catalyzer after the described regeneration is divided into three parts, 20～40% weight enter the first reaction zone, and 20～40% weight enter second reaction zone, and 20～60% weight enter the 4th reaction zone.
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