CN112299939A - Method and system for preparing olefin from methanol - Google Patents

Method and system for preparing olefin from methanol Download PDF

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Publication number
CN112299939A
CN112299939A CN202011109522.7A CN202011109522A CN112299939A CN 112299939 A CN112299939 A CN 112299939A CN 202011109522 A CN202011109522 A CN 202011109522A CN 112299939 A CN112299939 A CN 112299939A
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methanol
catalyst
gas
olefin
reactor
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CN112299939B (en
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南海明
任海君
谢君
刘明鑫
文尧顺
张世杰
闫锡军
林华东
夏婷婷
闫辉
金海峰
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Shenhua Engineering Technology Co ltd
China Shenhua Coal to Liquid Chemical Co Ltd
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Shenhua Engineering Technology Co ltd
China Shenhua Coal to Liquid Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • 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
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

The invention relates to the technical field of methanol to olefin, in particular to a method and a system for preparing olefin from methanol, wherein the method for preparing olefin from methanol comprises the following steps: (1) in the presence of cracking gas, raw materials containing methanol are contacted with a methanol-to-olefin catalyst to carry out a methanol-to-olefin reaction, so that olefin-containing product gas and a spent catalyst are obtained; (2) in the presence of oxygen-containing gas, carrying out regeneration reaction on the spent catalyst to obtain a regenerated catalyst; (3) mixing the regenerated catalyst with C4 +Hydrocarbon contacts to carry out cracking reaction to obtain the cracking gas and a semi-regenerated catalyst, and the semi-regenerated catalyst is divided into an a-strand agent and a b-strand agent; (4) circularly adding the b-ply agent into the methanol-to-olefin catalyst in the step (1)An agent; the a strands of agents are circularly mixed with the spent catalyst. The invention is in C4 +On the premise that the hydrocarbons provide enough cracking heat, the influence on the reaction of preparing the olefin from the methanol is avoided, and the total yield of the ethylene and the propylene is finally improved.

Description

Method and system for preparing olefin from methanol
Technical Field
The invention relates to the technical field of methanol to olefin, in particular to a method and a system for preparing olefin from methanol.
Background
After the Methanol To Olefins (MTO) technology is industrialized, the industrial scale is rapidly formed. At present, methanol to olefin has already occupied a remarkable proportion in the production capacity of ethylene and propylene in China.
C4 +The reaction of cracking olefin into ethylene and propylene is a strong endothermic reaction, and the yield of ethylene and propylene can be obviously improved. C commonly used at present4 +The olefin cracking technology comprises UOP OCP technology, middle petrochemical OCC technology and alkene cracking technology of large connected compounds, wherein the catalysts adopted by the OP OCP technology, the middle petrochemical OCC technology and the large connected compounds use ZSM-5 molecular sieves as main components, and the catalyst adopted by the large connected compounds uses SAPO-34 as a main component. On the other hand, the regenerated catalyst for preparing olefin from methanol enters the reactor under the high-temperature condition to initiate side reaction, so that the yield of the target product is reduced, and the regenerated catalyst is conveyed with C4 +The contact and the cracking reaction occur, on one hand, the yield of ethylene and propylene can be increased, the redundant heat carried by the ethylene and the propylene can be removed, the side reaction of a dilute phase section of the MTO reactor is inhibited, and the effect of killing two birds with one stone is achieved. Introducing C4 or C during the transportation of the regenerated catalyst4 +The material flow is a common means for improving the yield of ethylene and propylene and reducing the unit consumption of methanol. However, due to the limited amount of heat carried by the regenerated catalyst, only a small portion of the C from the downstream olefin separation unit is converted4 +Logistics, which makes the positive effect of the lifting means suppressed.
CN107043317A discloses a methanol-to-olefin device, specifically discloses the work flow of the device: after being preheated, the raw material methanol respectively enters two reactors 10 and contacts and reacts with the catalyst in the reactors 10. The product gas after reaction is separated from the catalyst by a three-stage cyclone separator, the catalyst generates coke after reaction, the activity is reduced, and the spent catalyst is formed. After being stripped, the spent catalysts in the two reactors 10 enter the same regenerator 20 through two paths respectively for regeneration (the spent catalyst inlets may be different inlets or the same inlet), the spent catalysts are in contact with oxygen in the air in the regenerator 20 for regeneration, coke on the catalysts is burned off, and the activity of the catalysts is recovered, so that the regenerated catalysts are obtained. The regenerated catalyst is led out from a regenerated catalyst outlet of the regenerator 20, and after independent steam stripping and cooling, the regenerated catalyst respectively enters the two reactors 10 for continuous reaction in two paths. In the process, the reaction regeneration system forms two paths of catalyst circulation, the circulation amount is respectively controlled, and a regenerator is shared. The product gases produced by the two reactors 10 enter different rapid cooling water washing devices after being heated.
CN102190548A discloses a method for increasing the yield of low carbon olefin in the process of preparing olefin from methanol, which comprises the steps of carrying out contact reaction of a raw material containing methanol and a catalyst in a fast fluidized bed to generate a product material flow I containing low carbon olefin and simultaneously form an inactivated catalyst, then feeding the inactivated catalyst into a regenerator for regeneration, feeding the regenerated catalyst into a riser reaction zone, and reacting the regenerated catalyst with a catalyst containing C4 +The hydrocarbon feedstock is contacted with the product and catalyst produced in the second fast fluidized bed reaction zone, with a catalyst comprising C4 +The hydrocarbon raw material is contacted with a second catalyst from the regenerator to generate a product material flow II containing low-carbon olefin and simultaneously form a catalyst of pre-carbon deposit; the catalyst of the pre-carbon deposit is returned to the first fast bed reaction area to react with the raw material methanol. In the method, firstly, the regeneration degree of the regenerated catalyst is not mentioned, namely whether the deactivated catalyst is completely regenerated or incompletely regenerated with a little carbon deposit, and the regeneration degree relates to whether the catalyst is effectively utilized in the whole process; in addition, the regenerated catalyst and C in the process4 +The hydrocarbon feedstock is contacted in a riser reaction zone wherein the catalyst forms a portion of the char, and the product formed and a portion of the char forming catalyst are passed into a second fast fluidized bed reaction zone where they are contacted with a catalyst comprising C4 +The hydrocarbon raw material and the second catalyst from the regenerator contact and react, and a small amount of low-carbon olefin products are generated due to the reaction in the riser reaction zone, the composition of the product gas competes with the later-entered raw material containing more than four carbon hydrocarbons, and the carbon deposition degree of the catalysts from two times is different, so that the improvement of the selectivity of the olefin is limited, and the rapid fluidization of the catalysts aggravates the abrasion of the catalysts, so that the catalyst consumption is increased.
In conclusion, the heat carried by the catalyst can be increased by increasing the circulating amount of the catalyst, but more spent catalyst enters the regenerator to increase the coke rate of the methanol-to-olefin reaction and reduce the selectivity of the total ethylene and propylene carbon.
Disclosure of Invention
The invention aims to solve the problems of high coke production rate and low total ethylene and propylene carbon selectivity of a methanol-to-olefin reaction in the prior art, and provides a method and a system for preparing olefins from methanol.
In order to achieve the above object, a first aspect of the present invention provides a method for producing olefins from methanol, comprising the steps of:
(1) in the presence of cracking gas, raw materials containing methanol are contacted with a methanol-to-olefin catalyst to carry out a methanol-to-olefin reaction, so that olefin-containing product gas and a spent catalyst are obtained;
(2) in the presence of oxygen-containing gas, carrying out regeneration reaction on the spent catalyst to obtain a regenerated catalyst;
(3) mixing the regenerated catalyst with C4 +Hydrocarbon contacts to carry out cracking reaction to obtain the cracking gas and a semi-regenerated catalyst, and the semi-regenerated catalyst is divided into an a-strand agent and a b-strand agent;
(4) circularly adding the b-strand agent into the methanol-to-olefin catalyst in the step (1); and circularly mixing the a-strands of agents into the spent catalyst.
The second aspect of the present invention provides a system for preparing olefins from methanol, including: a methanol-to-olefin reactor, a regenerator, a gas-solid separation reactor and a cracking reactor; wherein the content of the first and second substances,
the methanol-to-olefin reactor comprises a dense-phase bed layer, a dilute-phase section and a lifting pipe, wherein the dense-phase bed layer and the dilute-phase section are arranged in the reactor from bottom to top;
the regenerator is communicated with the dense-phase bed layer through a lifting pipe and is used for regenerating a catalyst to be regenerated;
the top of the gas-solid separation reactor is communicated with the dilute phase section and is used for separating the pyrolysis gas and the semi-regenerated catalyst;
the bottom of the gas-solid separation reactor is respectively communicated with the dense-phase bed layer and the lifting pipe;
the regenerator is communicated with the cracking reactor through a regenerant conveying pipe;
the cracking reactor is arranged outside the gas-solid separator and is communicated with the gas-solid separator; and/or
The cracking reactor is combined with a gas-solid separator.
According to the technical scheme, part of regenerated catalysts are shunted, one part of regenerated catalysts enters an MTO reactor for methanol catalytic reaction, and the other part of regenerated catalysts serving as recycling regenerants and spent catalysts enter a regenerator together for regeneration reaction, so that the circulation quantity of the catalysts is increased, and the coke rate is prevented from being improved; the recycling regenerant is also used as a heat carrier to remove heat in the process of regeneration and scorching, thereby greatly increasing C4 +The olefin treatment capacity further improves the yields of ethylene and propylene and reduces the unit consumption of methanol of olefin in unit mass;
the invention increases the circulation quantity of the regenerated catalyst to be C4 +The hydrocarbon cracking reaction provides enough heat; in at C4 +On the premise that the hydrocarbons provide enough cracking heat, the influence on the reaction of preparing the olefin from the methanol is avoided, and the total yield of the ethylene and the propylene is finally improved.
The regenerator of the invention can be provided with no heat transfer facility or a heat transfer facility at the minimum, thereby reducing the investment of the heat exchange facility of the methanol-to-olefin device.
Drawings
FIG. 1 is a schematic structural diagram of a system for producing olefins from methanol with a cracking reactor disposed outside a gas-solid separation reactor according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a methanol to olefins system incorporating a cracking reactor and a gas-solid separator according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a methanol to olefins system with a cracking reactor disposed in the regenerant transfer line according to an embodiment of the present invention;
FIG. 4 shows a schematic diagram of a system including two C's according to an embodiment of the present invention4 +The structure of the system for preparing olefin by methanol with a hydrocarbon injection port and two cracking reactors is schematically shown.
Description of the reference numerals
1. Regenerator 2, methanol-to-olefin reactor 3 and semi-regeneration stripper
4. First C4 +Hydrocarbon injection port 5, regeneration air inlet 6, methanol raw materialInlet port
7. A semi-regeneration stripping gas inlet 8, a to-be-regenerated stripping gas inlet 9 and a lifting pipe
10. Spent stripper 11, regeneration stripper 13 and regeneration air distributor
14. Raw material distributor 15, first regulating valve 16, second regulating valve
17. Third regulating valve 18, lifting gas inlet 19 and regeneration flue gas outlet
20. Olefin-containing product gas 22, cracking reactor 24 and gas-solid separation reactor
25. Conveying gas inlets 26, C4 +Hydrocarbon distributor 27, second C4 +Hydrocarbon injection port
201. Dense bed 202, dilute phase section 21, regenerant delivery pipe
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the present invention provides a method for producing olefins from methanol, comprising the steps of:
(1) in the presence of cracking gas, raw materials containing methanol are contacted with a methanol-to-olefin catalyst to carry out a methanol-to-olefin reaction, so that olefin-containing product gas and a spent catalyst are obtained;
(2) in the presence of oxygen-containing gas, carrying out regeneration reaction on the spent catalyst to obtain a regenerated catalyst;
(3) mixing the regenerated catalyst with C4 +Hydrocarbon contacts to carry out cracking reaction to obtain the cracking gas and a semi-regenerated catalyst, and the semi-regenerated catalyst is divided into an a-strand agent and a b-strand agent;
(4) circularly adding the b-strand agent into the methanol-to-olefin catalyst in the step (1); and circularly mixing the a-strands of agents into the spent catalyst.
In the invention, the semi-regenerated catalyst is divided into the a-strand agent and the b-strand agent, the a-strand agent is used as the recycling regenerant to carry out the regeneration reaction with the catalyst to be regenerated, the circulation amount of the catalyst is increased, the coke rate is prevented from being improved, and the recycling regenerant can also be used as a heat carrier to remove heat in the process of regeneration and coke burning. In addition, the device of the invention is not provided with heat removing facilities such as a steam generator or the like at the minimum, and the heat is mainly removed from the regenerator through a large circulating amount of the catalyst and supplies heat to the cracking reaction.
The invention can adjust the heat generated by catalyst regeneration by adjusting the circulation quantity of the spent catalyst, and can further adjust the heat generated in the regeneration process by controlling the regeneration degree of the catalyst so as to meet the heat requirement of the cracking reaction.
According to the invention, in order to avoid a large amount of catalyst entering the methanol-to-olefin reactor, the weight ratio of the a-ply agent to the b-ply agent in the step (4) is preferably 0.1-6:1, preferably 2.5-3: 1.
According to the invention, in order to ensure a sufficient exothermic heat of scorching, it is preferred that the weight ratio of the spent catalyst to the a-agent in step (2) is 0.1-6:1, preferably 2.5-3: 1.
In the invention, the heat generated by the regeneration reaction can be adjusted by adjusting the carbon fixation of the catalyst, so that the requirement of the cracking reaction on the heat is met. Under the preferable condition, the carbon content of the spent catalyst is 6 wt% -9 wt%, and the carbon content is preferably 7 wt% -8 wt%; the carbon content of the regenerated catalyst is 1 wt% -3 wt%, preferably 1.5 wt% -2.2 wt%; the carbon content of the semi-regenerated catalyst is 1.1-3.5 wt%, preferably 1.6-2.3%.
In a preferred embodiment of the invention, the spent catalyst has a carbon content of 7 wt% to 8 wt%; the carbon content of the regenerated catalyst is 1.5-2.2 wt%; the carbon content of the semi-regenerated catalyst is 1.6-2.3%.
The invention also relates toCan adjust CO/CO in flue gas of regeneration reaction2The ratio further adjusts the heat generated in the regeneration process, and the CO/CO in the flue gas under the optimal condition2The ratio is 2:1-1.5: 1.
In the present invention, the kind of the methanol to olefin catalyst is not particularly limited, and may be known to those skilled in the art. Preferably, in step (1), the methanol-to-olefin reaction conditions at least satisfy: the temperature is 450 ℃ and 500 ℃, and the pressure is 0.05-0.3 MPaG.
According to the invention, in step (2), the conditions of the regeneration reaction at least satisfy: the temperature is 650-690 ℃, and the pressure is 0.05-0.3 MPaG.
According to the invention, in step (3), the conditions of the cleavage reaction include: the temperature is 520 ℃ and 600 ℃, and the pressure is 0.05-0.3 MPaG.
In the present invention, in order to remove the flue gas carried in the catalyst, it is preferable that the method further comprises subjecting at least one of the spent catalyst, the regenerated catalyst and the semi-regenerated catalyst to a stripping treatment. In a preferred embodiment of the present invention, the method further comprises subjecting the spent catalyst, the regenerated catalyst and the semi-regenerated catalyst to stripping treatment respectively.
FIG. 1 is a schematic structural diagram of a system for producing olefins from methanol with a cracking reactor disposed outside a gas-solid separation reactor according to an embodiment of the present invention; FIG. 2 is a schematic diagram of a methanol to olefins system incorporating a cracking reactor and a gas-solid separator according to an embodiment of the present invention; FIG. 3 is a schematic diagram of a methanol to olefins system with a cracking reactor disposed in the regenerant transfer line according to an embodiment of the present invention; FIG. 4 shows a schematic diagram of a system including two C's according to an embodiment of the present invention4 +The structure of the system for preparing olefin by methanol with a hydrocarbon injection port and two cracking reactors is schematically shown. As shown in fig. 1 to 4, the present invention further provides a system for producing olefins from methanol, which comprises: a methanol-to-olefin reactor 2, a regenerator 1, a gas-solid separation reactor 24 and a cracking reactor 22; wherein the methanol-to-olefin reactor 2 comprises a dense-phase bed 201 and a dilute-phase section 202 which are arranged inside and sequentially arranged from bottom to top,and an externally disposed riser 9;
the regenerator 1 is communicated with the dense bed 201 through a riser 9 and is used for regenerating a catalyst to be regenerated;
the top of the gas-solid separation reactor 24 is communicated with the dilute phase section 202 and is used for separating the pyrolysis gas and the semi-regenerated catalyst;
the bottom of the gas-solid separation reactor 24 is respectively communicated with the dense bed 204 and the riser 9;
the regenerator 1 is communicated with the cracking reactor 22 through a regenerant delivery pipe 21;
the cracking reactor 22 is disposed outside the gas-solid separator 24 and is in communication with the gas-solid separator 24; and/or
The cracking reactor 22 is combined with a gas-solid separator 24.
Fig. 1 is a schematic structural diagram of a system for producing olefins from methanol, in which a cracking reactor is disposed outside a gas-solid separation reactor according to an embodiment of the present invention, and as shown in fig. 1, in an embodiment of the present invention, the cracking reactor 22 is disposed outside the gas-solid separator 24, and at this time, the retention time of the regenerated catalyst in the cracking reactor 22 is short and uniform, which is beneficial to suppressing secondary reactions such as hydrogen transfer.
FIG. 2 is a schematic diagram showing the structure of a methanol-to-olefin system in which a cracking reactor and a gas-solid separator are combined according to an embodiment of the present invention, as shown in FIG. 2, in an embodiment of the present invention, a cracking reactor 22 is combined with a gas-solid separator 24 without separately providing a cracking reactor, and C4 +The hydrocarbons are cracked in the gas-solid separator 24 and gas-solid separated at the same time, so that the regenerated catalyst has longer residence time and certain distribution in the cracking reaction place, C4 +The hydrocarbons are not easy to penetrate the bed layer, and the one-way conversion rate of the reaction is improved.
FIG. 3 is a schematic diagram of a system for producing olefins from methanol with a cracking reactor disposed on a regenerant transfer line according to an embodiment of the present invention, as shown in FIG. 3, in an embodiment of the present inventionThe cracking reactor is arranged separately, but C is4 +The cracking of the hydrocarbon is carried out on a regenerant delivery line, i.e. the regenerant delivery line is used as a cracking reactor.
FIG. 4 shows a schematic diagram of a system including two C's according to an embodiment of the present invention4 +A schematic diagram of a system for producing olefins from methanol with a hydrocarbon injection port and two cracking reactors is shown in FIG. 4. in a preferred embodiment of the present invention, two C's are provided4 +Hydrocarbon injection port (first C)4 + Hydrocarbon injection port 4 and second C4 +A hydrocarbon injection port 27) provided with two cracking reactors (a first cracking reactor 22 and a second cracking reactor) correspondingly, the first cracking reactor 22 is arranged outside the gas-solid separator 24 and has a higher cracking reaction temperature, and the second cracking reactor is combined with the gas-solid separator 24 (namely, the gas-solid reactor) and has a lower cracking reaction temperature, namely, a first C4 +C injected from hydrocarbon injection port 44 +The hydrocarbons are cracked in the first cracking reactor 22, the second C4 +C injected from hydrocarbon injection port 274 +The hydrocarbons are cracked in the second cracking reactor, and the system is suitable for feeding materials with different reaction temperatures at different positions and completing the cracking reaction.
In a preferred embodiment of the invention, after the mixture of the pyrolysis gas and the semi-regenerated catalyst obtained from the pyrolysis reaction is separated by a gas-solid separator, the obtained pyrolysis gas still contains part of the semi-regenerated catalyst; because the methanol-to-olefin reactor contains the gas-solid separation equipment, the cracked gas obtained by gas-solid separation is introduced into the dilute phase section 202 of the methanol-to-olefin reactor 2, so that the cracked gas and the catalyst can be further subjected to gas-solid separation, and the separated catalyst enters the methanol-to-olefin reactor for catalytic reaction.
In the invention, in order to strip off the flue gas carried in the spent catalyst, under the preferable conditions, the system further comprises a spent stripper 10 which is arranged on a pipeline communicated with the methanol-to-olefin reactor 2 and the riser 9 and is used for carrying out stripping treatment on the spent catalyst.
In the invention, in order to remove the flue gas carried in the regenerated catalyst, the regeneration device further comprises a regeneration stripper 11 which is arranged on a pipeline communicated with the regenerator 1 and the gas-solid separation reactor 24 and is used for carrying out stripping treatment on the regenerated catalyst under the preferable conditions.
In the present invention, in order to remove the flue gas carried in the semi-regenerated catalyst, under the preferred conditions, the present invention further comprises a semi-regenerated stripper 3, which is arranged on a pipeline connecting the gas-solid separation reactor 24 and the dense bed 201, and is used for stripping the spent catalyst.
The working process of the preferred embodiment of the present invention is described below with reference to fig. 1:
raw materials containing methanol enter a methanol-to-olefin reactor 2 through a methanol raw material inlet 6, are uniformly distributed and introduced into a dense-phase bed 201 through a raw material distributor 14, then contact with a catalyst in the presence of pyrolysis gas to perform a methanol-to-olefin reaction to obtain olefin-containing product gas and a spent catalyst, and the olefin-containing product gas enters a subsequent treatment process through a product gas outlet 20;
the spent catalyst is stripped of organic matters such as hydrocarbons and the like by a spent stripper 10 (wherein the regenerated stripping gas enters the spent stripper 10 through a spent stripping gas inlet 8), enters a riser 9 after the flow is regulated by a first regulating valve 15, and then enters a regenerator 1; the regeneration air enters the regenerator 1 from the regeneration air inlet 5 and enters the catalyst regeneration dense-phase bed layer through the regeneration air distributor 13, so that the catalyst to be regenerated is subjected to regeneration reaction to obtain a regenerated catalyst, and the regenerated flue gas generated by the regeneration reaction enters the subsequent treatment facility through the regenerated flue gas outlet 19;
the regenerated catalyst is stripped by the regeneration stripper 11 to remove organic matters such as hydrocarbons and the like, enters the cracking reactor 22 through the regenerant conveying pipe 21, and is mixed with the first catalyst C4 + Hydrocarbon injection port 4 for injecting C4 +The hydrocarbons contact in the cracking reactor 22 to carry out cracking reaction, the obtained cracking reaction product enters the gas-solid separator 24 to carry out gas-solid separation to obtain cracking gas and a semi-regenerated catalyst, and the cracking gas enters the dilute phase section 202 of the methanol-to-olefin reactor 2 through the cracking gas conveying pipe;
(4) the semi-regenerated catalyst is separated into a agent a and an agent b after organic matters such as hydrocarbons and the like carried by the semi-regenerated catalyst are removed by a semi-regenerated stripper 3 (wherein semi-regenerated stripping gas enters the semi-regenerated stripper 3 through a semi-regenerated stripping gas inlet 7); lift gas is injected into the lift pipe 9 from a lift gas inlet 18, under the action of the lift gas, the a-strand agent enters the lift pipe 9 through a third regulating valve 17, and enters the regenerator 1 for regeneration reaction after being lifted by the lift pipe 9 together with a spent catalyst from the methanol-to-olefin reactor 2;
the conveying gas is injected into the conveying pipe from the conveying gas inlet 25, and the b-strand agent is circularly added into the methanol-to-olefin catalyst through the second regulating valve 16 under the action of the conveying gas.
The methanol-to-olefin method provided by the invention is suitable for the current common methanol-to-olefin device, including but not limited to a typical device for preparing olefin from methanol at 180 ten thousand tons per year (methanol feeding scale).
The present invention will be described in detail below by way of examples. In the following examples, the methanol-to-olefin reaction was carried out in a 180-million ton/year methanol-to-olefin apparatus, and the methanol-to-olefin catalyst was SMC-001, which is a methanol-to-olefin catalyst produced by Shenhua coal-to-oil chemical Co., Ltd.
Example 1
As shown in fig. 1, the method for preparing olefin from methanol comprises the following steps:
(1) methanol enters a methanol-to-olefin reactor 2 through a methanol raw material inlet 6, is uniformly distributed and introduced into a dense phase bed 201 through a raw material distributor 14, is contacted with a methanol-to-olefin catalyst in the presence of pyrolysis gas to perform a methanol-to-olefin reaction (the temperature is 480 ℃, and the pressure is 0.14MPaG), so as to obtain olefin-containing product gas and a spent catalyst with the carbon content of 8 wt%, and the olefin-containing product gas enters a subsequent treatment process through a product gas outlet 20;
(2) the spent catalyst is stripped of organic matters such as hydrocarbons and the like by a spent stripper 10 (wherein the regenerated stripping gas enters the spent stripper 10 through a spent stripping gas inlet 8), enters a riser 9 after the flow is regulated by a first regulating valve 15, and then enters a regenerator 1; the regeneration air enters the regenerator 1 from the regeneration air inlet 5 and enters the catalyst regeneration dense-phase bed layer through the regeneration air distributor 13, so that the spent catalyst is subjected to regeneration reaction (the temperature is 680 ℃, and the pressure is 0.15MPaG) to obtain a regenerated catalyst with the carbon content of 2 wt%, and the regeneration flue gas generated by the regeneration reaction enters a subsequent treatment facility through the regeneration flue gas outlet 19;
(3) the regenerated catalyst is stripped by the regeneration stripper 11 to remove organic matters such as hydrocarbons and the like, enters the cracking reactor 22 through the regenerant conveying pipe 21, and is mixed with the first catalyst C4 + Hydrocarbon injection port 4 for injecting C4 +The hydrocarbons contact in a cracking reactor 22 to carry out cracking reaction (the temperature is 550 ℃, the pressure is 0.15MPaG), the obtained cracking reaction product enters a gas-solid separator 24 to carry out gas-solid separation to obtain cracking gas and a semi-regenerated catalyst with the carbon content of 2.5 wt%, and the cracking gas enters a dilute phase section 202 of a methanol-to-olefin reactor 2 through a cracking gas conveying pipe;
(4) the semi-regenerated catalyst is separated into an a-strand agent and a b-strand agent after organic matters such as hydrocarbons and the like carried by the semi-regenerated stripper 3 are removed (wherein semi-regenerated stripping gas enters the semi-regenerated stripper 3 through a semi-regenerated stripping gas inlet 7), and the weight ratio of the a-strand agent to the b-strand agent is 3: 1; lifting gas is injected into the lifting pipe 9 from a lifting gas inlet 18, under the action of the lifting gas, the a-strand agent enters the lifting pipe 9 through a third regulating valve 17, is lifted together with a spent catalyst from the methanol-to-olefin reactor 2 through the lifting pipe 9 and then enters the regenerator 1 for regeneration reaction, and the weight ratio of the a-strand agent to the spent catalyst is 3: 1;
the conveying gas is injected into the conveying pipe from the conveying gas inlet 25, and the b-strand agent is circularly added into the methanol-to-olefin catalyst through the second regulating valve 16 under the action of the conveying gas.
The proportions of the catalysts, the carbon contents, and the reaction results in this example are shown in Table 1.
Example 2
FIG. 2 is a schematic diagram of a methanol to olefins system incorporating a cracking reactor and a gas-solid separator according to an embodiment of the present invention; as shown in fig. 2, the method for preparing olefin from methanol is the same as the method in example 1, except that a cracking reactor is not separately provided, the cracking reactor is combined with a gas-solid separator, the cracking reaction and the gas-solid separation reaction are both performed in the gas-solid separator 24, and the cracking reaction conditions are as follows: the temperature was 550 ℃ and the pressure was 0.15 MPaG.
The proportions of the catalysts, the carbon contents, and the reaction results in this example are shown in Table 1.
Example 3
FIG. 3 is a schematic diagram of a methanol to olefins system with a cracking reactor disposed in the regenerant transfer line according to an embodiment of the present invention; as shown in fig. 3, the method for producing olefins from methanol is the same as the method of example 1, except that a cracking reactor is not separately provided, the cracking reaction is performed in a regenerant transfer pipe 21, and the cracking reaction conditions are as follows: the temperature was 550 ℃ and the pressure was 0.15 MPaG.
The proportions of the catalysts, the carbon contents, and the reaction results in this example are shown in Table 1.
Example 4
FIG. 4 is a schematic diagram of a methanol to olefins system having two cracking reactors, according to an embodiment of the present invention; as shown in FIG. 4, the methanol to olefin process was the same as that of example 1, except that the cracking reactor was provided with two (a first cracking reactor 22 and a second cracking reactor 24), and the system further included two C4 +Hydrocarbon injection port (first C)4 + Hydrocarbon injection port 4 and second C4 +Hydrocarbon injection port 27), first C4 +C injected from hydrocarbon injection port 44 +The hydrocarbons are subjected to a first cracking reaction, second C, in a first cracking reactor 224 +C injected from hydrocarbon injection port 274 +The hydrocarbons are subjected to a second cracking reaction in a second cracking reactor;
the first cracking reaction conditions are as follows: the temperature is 600 ℃, the pressure is 0.15MPaG, and the space velocity is 0.02h-1，
The second cracking reaction conditions are as follows: the temperature is 550 ℃, the pressure is 0.15MPaG, and the space velocity is 0.08h-1。
The proportions of the catalysts, the carbon contents, and the reaction results in this example are shown in Table 1.
Comparative example 1
A conventional methanol to olefins plant was used, i.e., the plant of example 1, except that: the semi-regenerated catalyst was introduced into the methanol to olefin reactor 2 without the pipe 17, and the semi-regenerated catalyst was not divided, and the ratio, carbon content and reaction results of each catalyst in this comparative example are shown in table 1.
TABLE 1 Main parameters and results
Figure BDA0002728123080000131
As can be seen from the results in Table 1, the method of the embodiment of the invention not only increases the circulating amount of the catalyst, but also improves the yield and selectivity of ethylene and propylene, reduces the coke rate of the catalyst, and reduces the unit consumption of methanol of olefin per unit mass; and heat transfer facilities such as a steam generator and the like are not needed to be arranged or are arranged at the minimum, so that the investment of the methanol-to-olefin device is reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A method for preparing olefin from methanol is characterized by comprising the following steps:
(1) in the presence of cracking gas, raw materials containing methanol are contacted with a methanol-to-olefin catalyst to carry out a methanol-to-olefin reaction, so that olefin-containing product gas and a spent catalyst are obtained;
(2) in the presence of oxygen-containing gas, carrying out regeneration reaction on the spent catalyst to obtain a regenerated catalyst;
(3) mixing the regenerated catalyst with C4 +Hydrocarbon is contacted to carry out cracking reaction to obtain the cracking gas and semi-regenerated catalyst, and the semi-regenerated catalyst is usedThe raw catalyst is divided into a strand agent and a strand agent;
(4) circularly adding the b-strand agent into the methanol-to-olefin catalyst in the step (1); and circularly mixing the a-strands of agents into the spent catalyst.
2. The method according to claim 1, wherein in step (4), the weight ratio of the a-ply agent to the b-ply agent is 0.1-6:1, preferably 2.5-3: 1.
3. The process according to claim 1 or 2, wherein in step (4), the weight ratio of the spent catalyst to the a-ply agent is 0.1-6:1, preferably 2.5-3: 1.
4. The method according to any one of claims 1 to 3, wherein the spent catalyst has a carbon content of 6 wt% to 9 wt%;
preferably, the carbon content of the regenerated catalyst is 1 wt% to 3 wt%;
preferably, the carbon content of the semi-regenerated catalyst is 1.1 wt% to 3.5 wt%.
5. The process of any one of claims 1-4, wherein in step (1), the methanol to olefin reaction conditions are at least: the temperature is 450 ℃ and 500 ℃, and the pressure is 0.05-0.3 MPaG;
preferably, in step (2), the conditions of the regeneration reaction at least satisfy: the temperature is 650 plus 690 ℃, and the pressure is 0.05-0.3 MPaG;
preferably, in step (3), the conditions of the cleavage reaction at least satisfy: the temperature is 520 ℃ and 600 ℃, and the pressure is 0.05-0.3 MPaG.
6. The method according to any one of claims 1 to 5, further comprising subjecting at least one of the spent catalyst, regenerated catalyst and semi-regenerated catalyst to a stripping treatment.
7. A system for producing olefins from methanol, the system comprising: a methanol-to-olefin reactor (2), a regenerator (1), a gas-solid separation reactor (24) and a cracking reactor (22); wherein the content of the first and second substances,
the methanol-to-olefin reactor (2) comprises a dense-phase bed layer (201) and a dilute-phase section (202) which are arranged inside and sequentially arranged from bottom to top, and a riser (9) arranged outside;
the regenerator (1) is communicated with the dense bed (201) through a riser (9) and is used for regenerating a spent catalyst;
the top of the gas-solid separation reactor (24) is communicated with the dilute phase section (202) and is used for separating the pyrolysis gas and the semi-regenerated catalyst;
the bottom of the gas-solid separation reactor (24) is respectively communicated with the dense bed layer (201) and the lifting pipe (9);
the regenerator (1) is communicated with the cracking reactor (22) through a regenerant conveying pipe (21);
the cracking reactor (22) is arranged outside the gas-solid separator (24) and is communicated with the gas-solid separator (24); and/or
The cleavage reactor (22) is combined with a gas-solid separator (24).
8. The system of any one of claim 7, further comprising a spent stripper (10) disposed on a pipeline of the methanol-to-olefin reactor (2) communicating with the riser (9) for stripping the spent catalyst.
9. The system according to claim 7 or 8, wherein the system further comprises a regeneration stripper (11) arranged on a pipeline of the regenerator (1) communicated with the gas-solid separation reactor (24) for stripping the regenerated catalyst.
10. The system according to any one of claims 7-9, wherein the system further comprises a semi-regenerative stripper (3) arranged on a pipeline of the gas-solid separation reactor (24) communicating with the dense bed (201) for stripping the spent catalyst.
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