CN102875283B - The method of low-carbon alkene is prepared by methyl alcohol and petroleum naphtha - Google Patents

The method of low-carbon alkene is prepared by methyl alcohol and petroleum naphtha Download PDF

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CN102875283B
CN102875283B CN201110193465.XA CN201110193465A CN102875283B CN 102875283 B CN102875283 B CN 102875283B CN 201110193465 A CN201110193465 A CN 201110193465A CN 102875283 B CN102875283 B CN 102875283B
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CN102875283A (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

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Abstract

The present invention relates to a kind of method being prepared low-carbon alkene by methyl alcohol and petroleum naphtha, mainly solve the problem that in prior art, yield of light olefins is low.The present invention mainly comprises the following steps by adopting: the raw material that (1) comprises petroleum naphtha enters the first reaction zone, and product stream and catalyzer enter settling vessel; Methanol feedstock enters second reaction zone, and product stream and catalyzer enter the 3rd reaction zone, and product stream and the catalyzer of generation enter settling vessel; (2) in settling vessel, gaseous stream enters centrifugal station, isolates the product comprising low-carbon alkene, C4 ~ C8 hydrocarbon mixture, and wherein the logistics of C4 ~ C8 hydrocarbon mixture enters the 4th reaction zone, and product stream and catalyzer enter the 3rd reaction zone; (3) in settling vessel, catalyzer enters revivifier, catalyzer after regeneration is divided into three parts, a part enters the first reaction zone, a part enters second reaction zone, the technical scheme that a part enters the 4th reaction zone solves the problems referred to above preferably, can be used in the industrial production of low-carbon alkene.

Description

The method of low-carbon alkene is prepared by methyl alcohol and petroleum naphtha
Technical field
The present invention relates to a kind of method being prepared low-carbon alkene by methyl alcohol and petroleum naphtha.
Technical background
Low-carbon alkene, i.e. ethene and propylene, be two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are produced by petroleum path, but due to the limited supply of petroleum resources and higher price, produce ethene by petroleum resources, the cost of propylene constantly increases.In recent years, people start to greatly develop the technology that alternative materials transforms ethene processed, propylene.Wherein, the important alternative materials 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, and as methyl alcohol, can be obtained by coal or Sweet natural gas, technique is very ripe, can realize the industrial scale of up to a million tonnes.Due to the popularity in oxygenatedchemicals source, add the economy transforming and generate light olefin technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), be particularly subject to increasing attention by the technique of preparing olefin by conversion of methanol (MTO).
Petroleum naphtha is a kind of light-end products, is cut corresponding cut by crude distillation or oil secondary processing and is obtained.Its boiling spread is determined according to need, is generally wider boiling range, as 20-220 DEG C.Petroleum naphtha is pyrolysis in tubular furnace preparing ethylene, and propylene and catalytic reforming produce the important source material of benzene,toluene,xylene.As cracking stock, in requiring petroleum naphtha to form, the content of alkane and naphthenic hydrocarbon is not less than 70% (volume).Naphtha catalytic pyrolysis preparing low-carbon alkene is then under catalyzer existent condition, carries out cracking to obtain the production process of low-carbon alkene to petroleum hydrocarbon.Compare with traditional tube furnace steam heat cracking, this process reaction temperature is about lower than steam cracking reaction 50 ~ 200 DEG C, and energy consumption significantly reduces; Cracking furnace pipe inwall coking rate also can reduce, thus can prolong operation cycle, increases the boiler tube life-span; Carbon emission simultaneously also can reduce, and alleviates pollution, and can adjust the product mix flexibly.
Technology and reactor that a kind of oxygenate conversion is low-carbon alkene is disclosed in US6166282, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu of gas speed has reacted, after rising to the fast subregion that internal diameter diminishes rapidly, special gas-solid separation equipment initial gross separation is adopted to go out most entrained catalyst.Due to reaction after product gas and catalyzer sharp separation, effectively prevent the generation of secondary reaction.Through analog calculation, compared with traditional bubbling fluidization bed bioreactor, needed for this fast fluidized bed reactor internal diameter and catalyzer, reserve all greatly reduces.
The multiple riser reaction unit disclosed in CN1723262 with central catalyst return is low-carbon alkene technique for oxygenate conversion, this covering device comprises multiple riser reactor, gas solid separation district, multiple 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.
Disclose a kind of method of methanol production propylene in EP0448000 and EP0882692, first methyl alcohol be converted into DME and water, then mixture is transported to First reactor, and add steam in this reactor.In the first reactor, methyl alcohol and (or) dme or its mixture and catalyst exposure react, catalyzer adopts the special ZSM-5 catalyzer containing ZnO and CdO, temperature of reaction 280 ~ 570 DEG C, pressure 0.01 ~ 0.1MPa, preparing with propylene is the product of main hydro carbons.Heavier product is as C 5 +hydrocarbon continues to carry out reacting the hydro carbons be converted into based on propylene in second reactor, after cooling, send separator back to.Product is compressed, refining further after can obtain the chemical grade propylene that purity is 97%.But adopt multiple fixed-bed reactor in this technique, because the activity of catalyzer limits, therefore need frequent blocked operation, and heat-obtaining problem is also very complicated.
US20070083071 discloses the processing method that a kind of hydrocarbon catalytic pyrolysis produces ethene, propylene, hydrocarbon feed is converted into the product comprising low-carbon alkene in catalytic cracker, then product stream is separated into C2 ~ C3 alkane, C2 ~ C3 alkene, the three kinds of logistics of C4+ hydrocarbon by series of process, C2 ~ C3 alkane is returned tube cracking furnace and carries out thermo-cracking, C4+ hydrocarbon returns catalytic cracker and carries out catalytic pyrolysis, finally obtains the ethene of higher yields, propylene product.The method adopts riser reactor, and reactant residence time is shorter, and low-carbon alkene product once through yield is lower.
Due to naphtha catalytic cracking and preparing olefin by conversion of methanol react object product---low-carbon alkene is identical, and main ingredient kind separately in product is roughly the same, the catalyst system adopted is also roughly the same, and from reaction mechanism angle, all there is the process being cracked into small molecules hydro carbons by macromole hydrocarbon or intermediate, therefore these two kinds of Technologies are had ready conditions and are coupled.The present invention solves this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the problem that the yield of light olefins that exists in prior art is not high, provides a kind of method being prepared low-carbon alkene by methyl alcohol and petroleum naphtha newly.The method is used for, in the production of low-carbon alkene, having the advantage that yield of light olefins is higher.
For solving the problem, the technical solution used in the present invention is as follows: a kind of method being prepared low-carbon alkene by methyl alcohol and petroleum naphtha, mainly comprise the following steps: at least one position of at least one opening for feed that the raw material that (1) comprises petroleum naphtha separates bottom the first reaction zone 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 comprising methyl alcohol enters second reaction zone, and the product stream of generation and catalyzer enter the 3rd reaction zone, and the product stream that the 3rd reaction zone generates and catalyzer enter settling vessel; (2) centrifugal station is entered after gaseous stream and catalyst separating in settling vessel, isolate the product comprising 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) in settling vessel, catalyzer enters revivifier regeneration after stripping, and the catalyzer after 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 technique scheme, described catalyzer comprises ZSM-5 molecular sieve, SiO 2/ Al 2o 3mol ratio is 10 ~ 100; Catalyzer coke content massfraction after described regeneration is 0.01 ~ 0.5%; Also comprise water vapour in described first reaction zone feeds, the weight ratio of water vapour and petroleum naphtha is 0.05 ~ 1.5: 1; Methyl alcohol is mainly in 3rd reaction zone feeds; Described petroleum naphtha boiling range is between 20 DEG C ~ 220 DEG C; In described first reaction zone, reaction conditions is: temperature of reaction is 570 ~ 670 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In second reaction zone, reaction conditions is: temperature of reaction is 480 ~ 600 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In 3rd reaction zone, reaction conditions is: temperature of reaction is 480 ~ 600 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 1 ~ 3 meter per second; In 4th reaction zone, reaction conditions is: temperature of reaction is 530 ~ 630 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and 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 bottom the 4th reaction zone or from least one opening for feed in axial direction separated; Catalyst activity sex index after described regeneration is greater than 0.8; Described first reaction zone is riser tube; Second reaction zone is riser tube; 3rd reaction zone is fast bed; 4th reaction zone is riser tube; Catalyzer after 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.
Regenerated catalyst activity index is for embodying the regeneration level of decaying catalyst, take live catalyst as benchmark, carry out relatively with the amount of catalytic conversion light naphthar each under rigid condition, method of calculation are: regenerated catalyst activity index=(the light naphthar amount that under light naphthar amount/certain condition that under certain condition, regenerated catalyst transforms, live catalyst transforms) × 100%.Described certain condition or rigid condition refer to employing fluidized-bed reactor, at the reaction conditions that temperature of reaction is 600 DEG C, reaction pressure counts 0 with gauge pressure, the gas phase residence time is 4 seconds.
ZSM-5 molecular sieve of the present invention can adopt method known in the field, as hydrothermal synthesis method, be prepared, described molecular sieve catalyst optionally load can have the metal of dehydrogenation functionality, the metal of dehydrogenation functionality is selected from least one in IB, IIB, VB, VIB, VIIB in the periodic table of elements or VIII, and the method for the metal load of dehydrogenation functionality on ZSM-5 molecular sieve can be adopted method known in the field, 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 the catalyst fines after shaping is placed in stoving oven and carries out roasting, after cooling, obtain catalyst sample.Binding agent can select SiO 2, Al 2o 3deng.
Adopt method of the present invention, four reaction areas is set, it is low-carbon alkene that first reaction zone is mainly used in naphtha catalytic cracking, second reaction zone is mainly used in converting methanol, 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 in the first reaction zone, the 4th reaction zone adopts axial admission mode, reduce feed partial pressure, to improving low-carbon alkene transformation efficiency.In the present invention, settling vessel and revivifier can be arranged apart or can coaxially arrange, the public settling vessel in first, second, third, fourth reaction zone.4th reaction zone provides reactant and catalyzer for the 3rd reaction zone, and play is the object that the 3rd reaction zone lowers the temperature simultaneously.Therefore, adopt method of the present invention, not only realize energy-optimised, and methyl alcohol and convert naphtha are prepared low-carbon alkene be coupled, transform the high-carbon hydrocarbon by product falling to generate simultaneously, reach the object improving 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 described regeneration is 0.01 ~ 0.5%; Also comprise water vapour in described first reaction zone feeds, the weight ratio of water vapour and petroleum naphtha is 0.05 ~ 1.5: 1; Methyl alcohol is mainly in 3rd reaction zone feeds; Described petroleum naphtha boiling range is between 20 DEG C ~ 220 DEG C; In described first reaction zone, reaction conditions is: temperature of reaction is 570 ~ 670 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In second reaction zone, reaction conditions is: temperature of reaction is 480 ~ 600 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In 3rd reaction zone, reaction conditions is: temperature of reaction is 480 ~ 600 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 1 ~ 3 meter per second; In 4th reaction zone, reaction conditions is: temperature of reaction is 530 ~ 630 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and 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 bottom the 4th reaction zone or from least one opening for feed in axial direction separated; Catalyst activity sex index after described regeneration is greater than 0.8; Described first reaction zone is riser tube; Second reaction zone is riser tube; 3rd reaction zone is fast bed; 4th reaction zone is riser tube; Catalyzer after 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, low-carbon alkene carbon base absorption rate can reach 65.06% weight, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1 is 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 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 fluid source line; 14 is that the first reaction zone outlet 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 3rd reaction zone outlet is slightly revolved; 21 is the first reaction zone feeds; 22 is 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 comprising petroleum naphtha separates bottom the first reaction zone 19 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 comprising methyl alcohol enters second reaction zone 10, the product stream generated and catalyzer enter the 3rd reaction zone 12, the product stream that 3rd reaction zone 12 generates and catalyzer enter settling vessel 17, centrifugal station is entered after gaseous stream and catalyst separating in 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 generated and catalyzer enter the 3rd reaction zone 12, in settling vessel 17, catalyzer enters revivifier 3 and regenerates after stripping, catalyzer after regeneration is divided into three parts, a part enters the first reaction zone 19, a part enters second reaction zone 10, a part enters the 4th reaction zone 23.
Below by embodiment, the invention will be further elaborated, but be not limited only to the 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 loaded metal quality accounts for catalyst quality is Cu:5.53; Zn:2.76; Co:1.68.The raw material comprising petroleum naphtha enters the first reaction zone bottom the first reaction zone, and product stream and the catalyzer of generation enter settling vessel, the raw material of methyl alcohol enters second reaction zone, the product stream generated and catalyzer enter the 3rd reaction zone, the product stream that 3rd reaction zone generates and catalyzer enter settling vessel, centrifugal station is entered after gaseous stream and catalyst separating in 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 generated and catalyzer enter the 3rd reaction zone, in settling vessel, catalyzer enters revivifier regeneration after stripping, catalyzer after regeneration is divided into three parts, 20% weight enters the first reaction zone, 20% weight enters second reaction zone, 60% weight enters the 4th reaction zone.First reaction zone is riser tube; Second reaction zone is riser tube; 3rd reaction zone is fast bed; 4th reaction zone is riser tube.Catalyzer coke content massfraction after regeneration is also comprise water vapour in the 0.01%, first reaction zone feeds, and the weight ratio of water vapour and petroleum naphtha is in the 1.5: 1, three reaction zone feeds be methyl alcohol, and petroleum naphtha composition is in table 1.In first reaction zone, reaction conditions is: temperature of reaction is 570 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 4 meter per seconds; In second reaction zone, reaction conditions is: temperature of reaction is 480 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 4 meter per seconds; In 3rd reaction zone, reaction conditions is: temperature of reaction is 482 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 1 meter per second; In 4th reaction zone, reaction conditions is: temperature of reaction is 530 DEG C, and reaction pressure counts 0.01 ~ MPa with gauge pressure, and gas phase linear speed is 4 meter per seconds.The logistics of C4 ~ C8 hydrocarbon mixture enters the 4th reaction zone bottom the 4th reaction zone.Catalyst activity sex index after 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 low-carbon alkene carbon base absorption rate is 59.28% weight.
[embodiment 2]
According to the condition described in embodiment 1 and step, catalyzer is ZSM-5, SiO 2/ Al 2o 3mol ratio is 10, and the raw material comprising petroleum naphtha enters the first reaction zone bottom the first reaction zone and along an opening for feed the first reaction zone axial direction due, is 1/2 first reaction zone height bottom this opening for feed distance first reaction zone.Catalyzer after 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 regeneration is also comprise water vapour in the 0.5%, first reaction zone feeds, and the weight ratio of water vapour and petroleum naphtha is 0.05: 1.In first reaction zone, reaction conditions is: temperature of reaction is 670 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 10 meter per seconds; In second reaction zone, reaction conditions is: temperature of reaction is 600 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 10 meter per seconds; In 3rd reaction zone, reaction conditions is: temperature of reaction is 600 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 3 meter per seconds; In 4th reaction zone, reaction conditions is: temperature of reaction is 630 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 10 meter per seconds.The logistics of C4 ~ C8 hydrocarbon mixture enters the 4th reaction zone bottom the 4th reaction zone and from the opening for feed in axial direction, and is 1/2 the 4th reaction zone height bottom this opening for feed distance the 4th reaction zone.Catalyst activity sex index after regeneration is 0.8.Keep the stability of catalyst flow control, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 62.49% weight.
[embodiment 3]
According to the condition described in embodiment 1 and step, catalyzer is ZSM-5, SiO 2/ Al 2o 3mol ratio is 70, and the raw material comprising petroleum naphtha enters the first reaction zone bottom the first reaction zone and along two opening for feeds the first reaction zone axial direction due, is respectively 1/3,1/2 first reaction zone height bottom two opening for feed distance the first reaction zones.Catalyzer after 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 regeneration is also comprise water vapour in the 0.05%, first reaction zone feeds, and the weight ratio of water vapour and petroleum naphtha is 0.5: 1.In first reaction zone, reaction conditions is: temperature of reaction is 650 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 7 meter per seconds; In second reaction zone, reaction conditions is: temperature of reaction is 560 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 6 meter per seconds; In 3rd reaction zone, reaction conditions is: temperature of reaction is 550 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 6.3 meter per seconds; In 4th reaction zone, reaction conditions is: temperature of reaction is 610 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 7 meter per seconds.The logistics of C4 ~ C8 hydrocarbon mixture enters the 4th reaction zone bottom the 4th reaction zone and from two opening for feeds in axial direction, and is respectively 1/3,1/2 the 4th reaction zone height bottom two opening for feed distance the 4th reaction zones.Catalyst activity sex index after regeneration is 0.94.Keep the stability of catalyst flow control, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 65.06% weight.
[embodiment 4]
According to the condition described in embodiment 1 and step, catalyzer is ZSM-5, SiO 2/ Al 2o 3mol ratio is 30, and the raw material comprising petroleum naphtha enters the first reaction zone bottom the first reaction zone and along three opening for feeds the first reaction zone axial direction due, is respectively 1/4,1/3,1/2 first reaction zone height bottom three opening for feed distance the first reaction zones.Catalyzer after 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 regeneration is also comprise water vapour in the 0.1%, first reaction zone feeds, and the weight ratio of water vapour and petroleum naphtha is 0.25: 1.In first reaction zone, reaction conditions is: temperature of reaction is 660 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and gas phase linear speed is 5 meter per seconds; In second reaction zone, reaction conditions is: temperature of reaction is 570 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and gas phase linear speed is 5 meter per seconds; In 3rd reaction zone, reaction conditions is: temperature of reaction is 560 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and gas phase linear speed is 4.8 meter per seconds; In 4th reaction zone, reaction conditions is: temperature of reaction is 615 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and gas phase linear speed is 4 meter per seconds.The logistics of C4 ~ C8 hydrocarbon mixture enters the 4th reaction zone bottom the 4th reaction zone and from two opening for feeds in axial direction, and is respectively 1/3,1/2 the 4th reaction zone height bottom two opening for feed distance the 4th reaction zones.Catalyst activity sex index after regeneration is 0.94.Keep the stability of catalyst flow control, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 60.67% weight.
[comparative example 1]
According to the condition described in embodiment 1 and step, just do not arrange the 4th reaction zone, low-carbon alkene carbon base absorption rate is 52.69% weight.
[comparative example 2]
According to the condition described in embodiment 1 and step, just do not arrange the 3rd reaction zone and the 4th reaction zone, low-carbon alkene carbon base absorption rate is 47.28% weight.
Obviously, adopt method of the present invention, the object improving yield of light olefins can be reached, there is larger technical superiority, can be used in the industrial production of low-carbon alkene.

Claims (5)

1. prepared a method for low-carbon alkene by methyl alcohol and petroleum naphtha, mainly comprise the following steps:
(1) at least one position of at least one opening for feed that the raw material comprising petroleum naphtha separates bottom the first reaction zone 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 comprising methyl alcohol enters second reaction zone, and the product stream of generation and catalyzer enter the 3rd reaction zone, and the product stream that the 3rd reaction zone generates and catalyzer enter settling vessel;
(2) centrifugal station is entered after gaseous stream and catalyst separating in settling vessel, isolate the product comprising 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) in settling vessel, catalyzer enters revivifier regeneration after stripping, and the catalyzer after 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;
Catalyzer coke content massfraction after described regeneration is 0.01 ~ 0.5%;
Also comprise water vapour in described first reaction zone feeds, the weight ratio of water vapour and petroleum naphtha is 0.05 ~ 1.5:1; Methyl alcohol is mainly in 3rd reaction zone feeds;
The logistics of the described C4 of comprising ~ C8 hydrocarbon mixture enters the 4th reaction zone bottom the 4th reaction zone or from least one opening for feed in axial direction separated;
Described first reaction zone is riser tube; Second reaction zone is riser tube; 3rd reaction zone is fast bed; 4th reaction zone is riser tube;
In described first reaction zone, reaction conditions is: temperature of reaction is 570 ~ 670 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In second reaction zone, reaction conditions is: temperature of reaction is 480 ~ 600 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In 3rd reaction zone, reaction conditions is: temperature of reaction is 480 ~ 600 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 1 ~ 3 meter per second; In 4th reaction zone, reaction conditions is: temperature of reaction is 530 ~ 630 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds.
2. prepared the method for low-carbon alkene according to claim 1 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. prepared the method for low-carbon alkene according to claim 1 by methyl alcohol and petroleum naphtha, it is characterized in that described petroleum naphtha boiling range is between 20 DEG C ~ 220 DEG C.
4. prepared the method for low-carbon alkene according to claim 1 by methyl alcohol and petroleum naphtha, it is characterized in that the catalyst activity sex index after described regeneration is greater than 0.8.
5. the method for low-carbon alkene is prepared according to claim 1 by methyl alcohol and petroleum naphtha, it is characterized in that the catalyzer after 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.
CN201110193465.XA 2011-07-12 2011-07-12 The method of low-carbon alkene is prepared by methyl alcohol and petroleum naphtha Active CN102875283B (en)

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