CN109336726A - A kind of technique of carbon four, light oil and coupling between methanol preparing propylene by catalytic cracking ethylene - Google Patents
A kind of technique of carbon four, light oil and coupling between methanol preparing propylene by catalytic cracking ethylene Download PDFInfo
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- CN109336726A CN109336726A CN201811440587.2A CN201811440587A CN109336726A CN 109336726 A CN109336726 A CN 109336726A CN 201811440587 A CN201811440587 A CN 201811440587A CN 109336726 A CN109336726 A CN 109336726A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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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
- Y02P20/584—Recycling of catalysts
Abstract
Carbon four, the technique of light oil (containing naphtha, stable light hydrocarbon, direct steaming gasoline, raffinating oil, gasoline etc.) and coupling between methanol preparing propylene by catalytic cracking ethylene are utilized the invention discloses a kind of.The technique includes feed material preparation units, catalytic cracking reaction-regeneration unit, separative unit, dry gas aromatisation unit.It present invention mainly solves with the heat coupled problem in carbon four, light oil preparing propylene by catalytic cracking ethylene and preparing propylene from methanol ethylene process, and realizes that plurality of raw materials comprehensively utilizes, can guarantee the continuity of production.The present invention can be used for producing in the commercial plant of propylene and ethylene, can alleviate the imbalance between supply and demand of propylene and promote the economic benefit of petroleum chemical enterprise.
Description
Technical field
The present invention relates to the techniques of a kind of carbon four, light oil and coupling between methanol preparing propylene by catalytic cracking ethylene, are applied to stone
Oily chemical field.
Background technique
Propylene is constantly in rare state as important industrial chemicals, and price is very high, as petroleum resources are more next
Deficienter, the raw material of propylene processed also becomes more and more rarer.Naphtha pyrolysis, catalytic cracking, methanol are mostly used on general industry
The approach such as propylene processed, dehydrogenating propane obtain propylene.In recent years, the research of butene cracking propylene was gradually taken seriously, still
Since source is limited, not yet it is applied in industry on a large scale.
Naphtha thermal cracking is the method for common, traditional ethylene processed while by-product propylene, using the method for thermal cracking
Ethylene processed, propylene need 800 DEG C or more of high temperature according to the reaction mechanism of free radical, and in product propylene proportion compared with
Low, therefore, researchers wish to improve productivity of propylene using the method for catalytic pyrolysis, and drop according to carbenium ion mechanism
Low energy consumption, the temperature of catalytic pyrolysis is mostly at 500~600 DEG C or so at present, and the yield of propylene is mostly 15~38%.
CN102603457B discloses the process units and technique of a kind of liquefied gas deep processing of C3, C4 production propylene.It should
Technique specifically includes that cracking unit, Vapor recovery unit unit, gas sub-unit and dehydrogenation unit.By the raw material liquefaction containing propane butane
Gas and liquefaction pneumatic transmission rich in butylene are to butene cracking production propylene units, butane preparing propene by oxidative dehydrogenation of propane and butylene list
Member, pyroreaction generates propylene under the action of catalyst and butylene, propylene send to the gentle sub-unit of Vapor recovery unit and finally obtain essence
Propylene, and butylene send to butene cracking unit as intermediate products and is cracked to form propylene.
CN101844960B discloses a kind of method of producting propylene by catalytic pyrolysis of liquefied gas, and this method is by normal domestic liquid
Change gas by depropanization, extracting rectifying etc. pretreatment after, with reaction product heat exchange after, be heated to 500~600 DEG C, 0.4MPa,
Weight space velocity 0.8h-1Under the conditions of, cracking reaction is carried out, after reaction product heat exchange is cooling, is obtained using the systems such as absorption, stable
High-knock rating gasoline, the liquefied gas rich in propylene and butylene.
CN107355508B discloses a kind of technique using liquefied gas processing and preparing hydrocarbon, including cracking reaction system, absorption
Systems stabilisation, aromatization reaction system, gas divide unstripped gas upgrading system, aromatic hydrocarbons purification system.
Summary of the invention
The purpose of the present invention is by the reaction in carbon four, light oil preparing propylene by catalytic cracking ethylene and preparing propylene from methanol ethylene
Thermal coupling altogether, convenient for control reaction temperature, is suitable for plurality of raw materials.
The following technical solution is employed for the technical problems to be solved by the invention to realize:
The technique of a kind of carbon four, light oil and coupling between methanol preparing propylene by catalytic cracking ethylene, specific features include following step
It is rapid:
Material carbon four enters pretreatment unit, and the light components such as propylene, propane contained in carbon four pass through three tower of decarburization from tower
Top distills, and is sent in the dethanizer of gas subsystem；And the original of carbon four and the above light hydrocarbon component as catalytic cracking reaction
Material enters cracking reaction system.
By pretreated carbon four and light oil, methanol mixing, the pre- of catalytic cracking reaction unit is pumped into through charging
Hot device, improves temperature, subsequently into heating furnace, being heated to 450~650 DEG C of reaction initiation temperature, the mixed raw material of high temperature
Enter catalyst for cracking bed at the top of the cracking reactor, occurs the reaction such as cracking, hydrogen migration, disproportionation, aromatisation, carbon four and gently
Matter oil catalytic cracking reaction is based on absorbing heat, and the reaction of preparing propylene from methanol ethylene is based on heat release.Both reaction heat effects
Coupling effect, can be adjusted by adjusting the ratio of raw material, to control bed temperature.Reaction product is from reactor bottom stream
Out, into feed preheater, heat is provided for it.Catalytic cracking catalyst is through meeting after reaction after a period of time in this technique
Gradually green coke needs to be arranged regenerative system and regenerates to the catalyst in this technique, and there are two functions for the regenerative system: first is that
To provide carbon containing catalyst for cracking to recycle service, second is that providing recycle service for carbon containing aromatized catalyst.Two kinds are urged
Agent is all the metal or nonmetallic modifying catalyst based on ZSM-5 molecular sieve, the range for burning temperature is all 380~
520℃.Regeneration technology process is as follows: by air and nitrogen according to a certain percentage (control range of air content are as follows: 0~
It 100V%) mixes, enters recycle gas compressor pressurization, preheating later, into heating furnace, 380~520 DEG C are heated to, from reaction
Enter catalyst bed at the top of device and carries out coke burning regeneration.For balanced reaction heat, partial regeneration air can without heating furnace, from
Compressor outlet directly enters reactor from the side feed inlet of reactor.
Catalytic cracking reaction enters after supercooling, compression with two bursts of reaction products of dry gas aromatization separates list
Member, separative unit are made of absorbing-stabilizing system and gas fractionating system, and reaction product initially enters absorbing-stabilizing system, product
In dry gas through absorption, a part go out from absorption tower top row, a part return dry gas aromatization reactor in.In reaction product
Liquefied gas component by desorption, be ejected into stabilizer by rectifying action from stabilizer, by pump pressurization be sent to gas
Subsystem.Contain isobutene in cleavage reaction product, can enter in stabilizer with liquefied gas component, in the middle and upper part of stabilizer
One section of MTBE synthetic catalyst is set, and another strand of material benzenemethanol of MTBE synthesis, it is fed from the middle part of stabilizer, with isobutene
It reacts on MTBE synthetic catalyst, generates MTBE, MTBE and gasoline come out from stabilizer bottom together, reconcile as gasoline
Group is distributed to tank field.Containing propylene, propane, butylene, butane and a small amount of C2 component in liquefied gas from stabilizer, enter
Gas subsystem, by principles of rectification, propylene is purified in propylene rectification tower A, B, and for purity up to 99.7%, purified propylene oxide can
Up to 95% or more, butane and butylene come out from depropanizing tower bottom, and a part is sent to tank field as product, and a part returns to cracking
In reactor, the reaction of butene cracking propylene is participated in.
The dry gas being ejected from absorption tower enters dry gas aromatisation unit, after preheating, into heating furnace, is heated to
After dry gas aromatization temperature, enter in aromatization reactor at the top of the aromatization reactor, the reactor be equipped with side line into
The reaction such as overlapping, aromatisation, isomerization occurs on aromatized catalyst bed for material, dry gas, generates the gasoline tune that RON is greater than 94
With component, liquefied petroleum gas and poor alkene dry gas, reaction product enters dry gas feed preheater from reactor bottom outflow, mentions for it
Heating load is mixed into separative unit by heat-exchanger rig and catalytic cracking reaction products.
The technique of a kind of carbon four, light oil and coupling between methanol preparing propylene by catalytic cracking ethylene, it is characterised in that: former
Material light oil be with light dydrocarbon~carbon ten for main component lighter hydrocarbons (containing naphtha, direct steaming gasoline, raffinate oil and stable light hydrocarbon,
Gasoline etc.).
The technique of a kind of carbon four, light oil and coupling between methanol preparing propylene by catalytic cracking ethylene, it is characterised in that: split
Solution reaction catalyst used is using ZSM-5 molecular sieve as main component, and by metal or nonmetallic modifying and be made, heap is close
Degree is in 0.63~0.73 ton/cubic metre, and 450~650 DEG C of reaction temperature, pressure is 0.1~1.0MPa, 0.1~5h of air speed-1。
The technique of a kind of carbon four, light oil and coupling between methanol preparing propylene by catalytic cracking ethylene, it is characterised in that: urge
Change cracking reactor be fixed bed, be divided into two sections or two sections or more and load, i.e., there are two or more than two reaction zones, it is built-in
Preparing propylene by catalytic cracking catalyst for ethylene, the number of reactor are 2 or 2 or more, guarantee the continuity of production.
Detailed description of the invention
Fig. 1 is feed material preparation units of the present invention, catalytic cracking reaction-regeneration unit, separative unit, dry gas aromatisation list
The process flow chart of member.
1- raw material liquefied gas head tank, 2- raw material liquefied gas feed pump, three tower feed preheater of 3- decarburization, 4- decarburization three
Tower, three tower top cooler of 5- decarburization, three return tank of top of the tower of 6- decarburization, three tower reflux pump of 7- decarburization, three tower reboiler of 8- decarburization, 9-
Material benzenemethanol head tank, 10- material benzenemethanol feed pump, 11- raw material C5C6 head tank, 12- raw material C5C6 feed pump, 13- cracking
Feed preheater, 14- crack heating furnace, 15- cracking reactor, and 16- cracks heating furnace, 17- cracking reactor, 18- cracking original
Expect preheater, 19- aromatisation heating furnace, 20- aromatization reactor, 21- aromatisation feed preheater, 22- air cooler, 23- water
Cooler, 24- rich gas compressor, 25- rich gas water cooler, 26- liquid separation tank, 27- absorption and desorption tower, 28- desorption tower reboiler；29-
Stabilizer feed pump, 30- stabilizer, 31- stablize tower top cooler, and 32- stablizes return tank of top of the tower, and 33- stablizes tower top return pump,
34- stabilizer reboiler, 35- stablize column bottoms pump, 36- gasoline water cooler, 37- depropanizing tower feed exchanger, 38- depropanization
Tower, 39- depropanization tower top cooler, 40- depropanization return tank of top of the tower, 41- depropanization tower top return pump, 42- depropanizing tower is again
Boil device；43- liquefied gas product water cooler, 44- dethanizer, 45- deethanization tower top cooler, 46- deethanization return tank of top of the tower,
47- deethanization tower top return pump, 48- deethanizer reboiler, 49- propylene rectification tower A, 50- propylene rectification tower A reboiler, 51-
Bromopropane product pump, 52- bromopropane product cooler, 53- propylene rectification tower B column bottoms pump, 54- propylene rectification tower B, 55- propylene rectifying
Tower B pushes up cooler, 56- propylene rectification tower B return tank；57- propylene rectification tower B reflux pump, 58- absorb midsection extraction cooling
Device, 59- absorb midsection and extract reflux pump, 60- reaction product liquid separation tank, 61- reaction product liquid pump out.
Fig. 2 is the flow chart of regenerative system of the present invention.
62- regeneration air water cooler, 63- recycle gas compressor inlet buffer, 64- recycle gas compressor.
Specific embodiment
In order to be apparent to the technical means, the creative features, the aims and the efficiencies achieved by the present invention, below with reference to tool
Body diagram, the present invention is further explained.
The present embodiment is the 300000 tons/year of stable light hydrocarbon liquefied gas methanol oxidations cracking propylene dress processed for building Mr. Yu refinery
It sets, which includes feed material preparation units, catalytic cracking reaction-regeneration unit, separative unit, dry gas aromatisation unit.It adopts
Process flow chart such as attached drawing 1, regeneration flow chart are as shown in Figure 2.
Raw material is stable light hydrocarbon, liquefied gas, methanol, and feedstock property is as follows:
1 raw material stable light hydrocarbon property of table
| Carbon number | N-alkane | Isoparaffin | Total alkane |
| C3 | 0.3 | 0.0 | 0.3 |
| C4 | 2.5 | 2.2 | 4.7 |
| C5 | 9.6 | 4.6 | 14.2 |
| C6 | 15.6 | 6.2 | 21.8 |
| C7 | 17.4 | 8.9 | 26.2 |
| C8 | 15.1 | 10.2 | 25.3 |
| C9 | 1.3 | 6.1 | 7.5 |
| C10 | 0.0 | 0.1 | 0.1 |
| Summation | 61.8 | 38.2 | 100.0 |
2 raw material liquefied gas property of table
3 material benzenemethanol property of table
| Project | Property |
| Purity | > 99.5% |
| Molecular formula | CH3OH |
| Molecular weight | 32 |
| Density (0 DEG C), g/ml | 0.8100 |
| Boiling point, DEG C | 64.6 |
| Specific heat, kcal/ DEG C of mol | 18.4 |
| The combustion heat, kcal/mol | 174 |
| Flash-point, DEG C | 9.5 (silent), 16 (openings) |
Raw material liquefied gas comes raw material liquefied gas head tank (1) from tank field or other units, feeds through raw material liquefied gas
Enter three tower feed preheater (3) of decarburization after pumping (2) pressurization, it is preheated, into three tower of decarburization (4), C3 and following light component from
Top fractionation, which comes out, enters three tower top cooler (5) of decarburization, and temperature enters three return tank of top of the tower of decarburization (6) after being cooled to room temperature,
The C3 of room temperature liquid and following light component, a part return to overhead reflux, and a part enters the depropanizing tower of gas subsystem.With fourth
C4 component based on alkane and butylene comes out in three tower of decarburization (4) bottom, into after the heat exchange of three tower feed preheater (3) of decarburization, into
Enter catalytic cracking reaction system.Three tower of decarburization (4) is provided with three tower reboiler of decarburization (8).
Material benzenemethanol comes material benzenemethanol head tank (9) from tank field, enters by material benzenemethanol feed pump (10) pressurization and urges
Change cracking reaction system.
Raw material C5C6 comes raw material C5C6 head tank (11) from tank field or other units, by raw material C5C6 feed pump (12)
After being mixed after pressurization with the butane butylene of material benzenemethanol, three tower of decarburization (4) bottom, into cracking stock preheater (13) or (18),
After preheated, into cracking heating furnace (16) or (19), after temperature is increased to 450~650 DEG C, into cracking reactor (17) or
(20), it reacts on catalyst bed, reaction product comes out from cracking reactor bottom, into cracking stock preheater
(13) or after (18) heat exchange, then successively enter air cooler (22) and water cooler (23), temperature is cooled to room temperature, subsequently into reaction
Product liquid separation tank (60), gas phase comes out from tank deck, and into rich gas compressor (24), liquid phase comes out from tank bottom passes through reaction product liquid
Body pumps (61), and stabilizer (30) are sent to after pressurization.The material come out from compressor passes through rich gas water cooler (25), and temperature is cooled to
After room temperature, enters back into and carry out liquid separation in liquid separation tank (26).Gas phase comes out at the top of liquid separation tank (26), into absorption and desorption tower
(27), liquid phase comes out from liquid separation tank (26) bottom, after being pressurized by stabilizer feed pump (29), into stabilizer (30).
The absorbent of absorption and desorption tower (27) is the gasoline come out from stabilizer (30) bottom, after cooling, by stabilizer bottom
Pump (35) is sent at the top of absorption and desorption tower (27).Absorption and desorption tower (27) is provided with middle section extraction reflux, and middle section Extract is from tower
After side is released, into midsection extraction cooler (58) is absorbed, temperature is cooled to 35 DEG C, extracts out into midsection is absorbed
It is returned in tower after reflux pump (59) pressurization.Desorption tower reboiler (28) are arranged in absorption and desorption tower (27).Dry gas comes out from tower top, and one
Part goes out device, and a part enters dry gas aromatisation unit, and the BTX aromatics oil of tower bottom enters stabilizer (30).
One section of MTBE synthetic catalyst is arranged in the middle part of stabilizer (30), and methanol is fed from the middle part of stabilizer, with liquefaction
Synthetic reaction occurs on MTBE catalyst for the isobutene in gas, and the MTBE of generation, which is mixed out at stabilizer bottom with gasoline, to be filled
It sets.Stabilizer reboiler (34) are arranged in the tower tower bottom.Liquefied gas component comes out from tower top rectifying, by stablizing tower top cooler
(31), temperature is cooled to room temperature, and into stablizing return tank of top of the tower (32), liquid phase component goes out from return tank of top of the tower (32) bottom is stablized
Come, by stablizing tower top return pump (33) pressurization, a part flows back into tower, and another part enters gas subsystem.Gasoline is from tower bottom
Out, after gasoline water cooler (36) is cooled to room temperature, a part goes out device as product, and a part enters as absorbent
Absorption and desorption tower (27).
The dry gas come out at the top of from absorption and desorption tower (27), a portion are pre- by aromatisation feed preheater (21)
Heat enters back into aromatisation heating furnace (19), and temperature is increased to 160~350 DEG C, into aromatization reactor (20), dry gas aromatization
Change product to come out from reactor bottom, into after aromatisation feed preheater (21) heat exchange, be mixed with cleavage reaction product
Into air cooler (22).
From three tower reflux pump (7) of decarburization and stablize tower top return pump (33) come C4 and following components be mixed into depropanization
Tower feed exchanger is preheated in (37), and subsequently into depropanizing tower (38), C3 and following components are distilled from tower top, into
Enter depropanization tower top cooler (39), after temperature is as cold as room temperature, into depropanization return tank of top of the tower (40), then through depropanization tower top
After reflux pump (41) pressure-raising, a part flows back into tower, and another part enters dethanizer (44).And C4 component comes out from tower bottom,
Into after heat exchange in depropanizing tower feed exchanger (37), a part returns to cracking reactor, and another part enters liquefied gas production
Product water cooler (43), temperature go out device after being cooled to room temperature.After C3 and following components enter dethanizer (44), C2 and with the following group
Divide and distilled from tower top, into deethanization tower top cooler (45), after being as cold as room temperature, into deethanization return tank of top of the tower
(46) in, gas phase comes out from tank deck, into gas train.Liquid phase comes out from tank bottom, increases by deethanization tower top return pump (47)
After pressure, into flowing back in tower, which is arranged reboiler (48).C3 component comes out from dethanizer (44) bottom, into propylene essence
Evaporate in tower A (49), propylene rectification tower A (49) and propylene rectification tower B (54) are a set of Distallation systms, two tower cooperations complete propane with
Reboiler (50) are arranged in the bottom of the separation of propylene, propylene rectification tower A (49), and the gas phase at the top of propylene rectification tower A (49) enters
The liquid phase of the tower reactor of propylene rectification tower B (54), propylene rectification tower B (54) bottom comes out from tower bottom, passes through propylene rectification tower B tower bottom
After pumping (53) pressure-raising, into the top propylene rectification tower A (49), the gas phase at the top of propylene rectification tower B (54) enters propylene rectification tower B
It pushes up cooler (55), room temperature is arrived after supercooling, into propylene rectification tower B return tank (56), liquid phase comes out from tank bottom, passes through third
After alkene rectifying column B reflux pump (57), for a part as flowing back into tower, another part goes out device as product propylene.Propane
It comes out, is entered in bromopropane product cooler (52) afterwards by bromopropane product pump (51), temperature is cold from propylene rectification tower A (49) bottom
But to entering tank field after room temperature.
After catalyst inactivation in a reactor, which is switched to regenerative system, regenerative system process is as follows:
Air and nitrogen are by respective flowmeter, after adjusting according to the range of AIR Proportional 0~100% (V), into circulation air pressure
After contracting machine (64) pressure-raising, it is sent into cracking stock preheater (13) or (18) or aromatisation feed preheater (21), it is preheated, so
380~480 DEG C are increased into cracking heating furnace (14) or (16) or aromatisation heating furnace (19), temperature afterwards, enters back into cracking
Reactor (15) or (17) or aromatization reactor (20), burn reaction, the regenerated flue gas of high temperature on catalyst bed
It is come out from reactor bottom, into heat exchange in cracking stock preheater (13) or (18) or aromatisation feed preheater (21), so
Enter regeneration air water cooler (62) temperature afterwards and be cooled to room temperature, into recycle gas compressor inlet buffer (63), passes through
The regeneration air of buffering enters recycle gas compressor (64), and the regenerative system of a circulation is formed with ozone and nitrogen.
It is provided with emptying at the top of recycle gas compressor inlet buffer (63), extra flue gas can be emitted from top drop out line.
The catalyst that cracking reaction uses is metal or nonmetallic modifying ZSM-5 molecular sieve catalyst, air speed 0.2~
5h-1.The one way period 20~25 days, the regeneration period was less than 7 days.
The catalyst that dry gas aromatization reactor uses is metal or nonmetallic modifying ZSM-5 molecular sieve catalyst, sky
0.5~3h of speed-1.The one way period 60~90 days, the regeneration period was less than 7 days.
Using above-mentioned process and catalyst, following product distribution is obtained:
| Serial number | Product | Form (w) % | Explanation |
| 1 | Dry gas+loss+coke | 6 | |
| 2 | Propylene | 19 | |
| 3 | Propane | 5 | |
| 4 | Liquefied gas | 17 | |
| 5 | Gasoline | 53 | RON82 |
| It amounts to | 100 |
Various equipment employed in the present invention, are all conventional equipments used in the production technology of this field, and equipment
Operating parameter etc. is carried out according to routine operation, and special feature is had no.
Basic principles and main features and advantage of the invention have been shown and described above.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and above embodiments and description description merely illustrates the principles of the invention,
Without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes and improvements are all
It falls into scope of the claimed invention, the claimed scope of the invention is by appended claims and its equivalent circle
It is fixed.
Claims (4)
1. the technique of a kind of carbon four, light oil and coupling between methanol preparing propylene by catalytic cracking ethylene, specific features the following steps are included:
(1) material carbon four enters pretreatment unit, and the light components such as propylene, propane contained in carbon four pass through three tower of decarburization from tower top
It distills, is sent in the dethanizer of gas subsystem；And the raw material of carbon four and the above light hydrocarbon component as catalytic cracking reaction
Into cracking reaction system.
(2) by pretreated carbon four and light oil, methanol mixing, the preheating of catalytic cracking reaction unit is pumped into through feeding
Device improves temperature, subsequently into heating furnace, being heated to 450~650 DEG C of reaction initiation temperature, the mixed raw material of high temperature from
Enter catalyst for cracking bed at the top of cracking reactor, the reaction such as cracking, hydrogen migration, disproportionation, aromatisation, carbon four and lightweight occurs
Oily catalytic cracking reaction is based on absorbing heat, and the reaction of preparing propylene from methanol ethylene is based on heat release.Both reaction heat effects
Coupling effect can be adjusted by adjusting the ratio of raw material, to control bed temperature.Reaction product is from reactor bottom stream
Out, into feed preheater, heat is provided for it.Catalytic cracking catalyst is through meeting after reaction after a period of time in this technique
Gradually green coke needs to be arranged regenerative system and regenerates to the catalyst in this technique, and there are two functions for the regenerative system: first is that
To provide carbon containing catalyst for cracking to recycle service, second is that providing recycle service for carbon containing aromatized catalyst.Two kinds are urged
Agent is all the metal or nonmetallic modifying catalyst based on ZSM-5 molecular sieve, the range for burning temperature is all 380~
520℃.Regeneration technology process is as follows: by air and nitrogen according to a certain percentage (control range of air content are as follows: 0~
It 100V%) mixes, enters recycle gas compressor pressurization, preheating later, into heating furnace, 380~520 DEG C are heated to, from reaction
Enter catalyst bed at the top of device and carries out coke burning regeneration.For balanced reaction heat, partial regeneration air can without heating furnace, from
Compressor outlet directly enters reactor from the side feed inlet of reactor.
(3) two bursts of reaction products of catalytic cracking reaction and dry gas aromatization enter separative unit after supercooling, compression,
Separative unit is made of absorbing-stabilizing system and gas fractionating system, and reaction product initially enters absorbing-stabilizing system, in product
Dry gas through absorption, a part go out from absorption tower top row, a part return dry gas aromatization reactor in.In reaction product
Liquefied gas component is ejected by rectifying action from stabilizer by desorption into stabilizer, is sent to gas point by pumping pressurization
System.Contain isobutene in cleavage reaction product, can enter in stabilizer with liquefied gas component, be set in the middle and upper part of stabilizer
One section of MTBE synthetic catalyst is set, and another strand of material benzenemethanol of MTBE synthesis exists from the charging of the middle part of stabilizer with isobutene
It reacts on MTBE synthetic catalyst, generates MTBE, MTBE and gasoline come out from stabilizer bottom together, as gasoline reconciliation group
It is distributed to tank field.Containing propylene, propane, butylene, butane and a small amount of C2 component in liquefied gas from stabilizer, into gas
Subsystem, by principles of rectification, propylene is purified in propylene rectification tower A, B, and for purity up to 99.7%, purified propylene oxide is reachable
95% or more, butane and butylene come out from depropanizing tower bottom, and a part is sent to tank field as product, and a part is anti-back to cracking
It answers in device, participates in the reaction of butene cracking propylene.
(4) dry gas being ejected from absorption tower enters dry gas aromatisation unit, after preheating, into heating furnace, is heated to
After dry gas aromatization temperature, enter in aromatization reactor at the top of the aromatization reactor, the reactor be equipped with side line into
The reaction such as overlapping, aromatisation, isomerization occurs on aromatized catalyst bed for material, dry gas, generates the gasoline tune that RON is greater than 94
With component, liquefied petroleum gas and poor alkene dry gas, reaction product enters dry gas feed preheater from reactor bottom outflow, mentions for it
Heating load is mixed into separative unit by heat-exchanger rig and catalytic cracking reaction products.
2. the technique of a kind of carbon four according to claim 1, light oil and coupling between methanol preparing propylene by catalytic cracking ethylene,
Be characterized in that: raw material light oil be with light dydrocarbon~carbon ten for main component lighter hydrocarbons (containing naphtha, direct steaming gasoline, raffinate oil with
And stable light hydrocarbon, gasoline etc.).
3. the technique of a kind of carbon four according to claim 1, light oil and coupling between methanol preparing propylene by catalytic cracking ethylene,
Be characterized in that: catalyst used in cracking reaction is using ZSM-5 molecular sieve as main component, by metal or nonmetallic modifying
And be made, heap density is in 0.63~0.73 ton/cubic metre, and 450~650 DEG C of reaction temperature, pressure is 0.1~1.0MPa, air speed
0.1~5h-1。
4. the technique of a kind of carbon four according to claim 1, light oil and coupling between methanol preparing propylene by catalytic cracking ethylene,
Be characterized in that: catalytic cracking reaction device be fixed bed, be divided into two sections or two sections or more and load, i.e., there are two or it is more than two
Reaction zone, built-in preparing propylene by catalytic cracking catalyst for ethylene, the number of reactor are 2 or 2 or more, guarantee production
Continuity.
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