CN109721447A - A method of olefin product is prepared using ciculation fluidized bed reaction technique - Google Patents
A method of olefin product is prepared using ciculation fluidized bed reaction technique Download PDFInfo
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- CN109721447A CN109721447A CN201711024043.3A CN201711024043A CN109721447A CN 109721447 A CN109721447 A CN 109721447A CN 201711024043 A CN201711024043 A CN 201711024043A CN 109721447 A CN109721447 A CN 109721447A
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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
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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
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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Abstract
The present invention provides a kind of using ciculation fluidized bed reaction technique by methanol or dimethyl ether for the method for olefin product, this method carries out in the reaction system for including fluidized-bed reactor and regenerator, use the raw material comprising methanol, dimethyl ether or methanol and the mixture of dimethyl ether, it is reacted under the catalytic action comprising ZSM-5 catalyst in the fluidized-bed reactor, generates the product mix gas comprising olefin product；During carrying out at least part of the reaction, regeneration step is carried out to the catalyst of carbon distribution.
Description
Technical field
The present invention relates to chemical catalyst and technology fields more particularly to a kind of ciculation fluidized bed reaction technique of utilization by first
Alcohol or dimethyl ether for olefin product method.
Background technique
Ethylene, propylene, butylene, amylene etc. are the important basic chemical industry raw materials of modern chemical industry, as China its people pass through
The continuous improvement for integral level of helping, the especially fast development of modern chemical industry, to bases such as ethylene, propylene, amylene, butylene
The demand of industrial chemicals increasingly rises.
The basic chemical industries raw material such as ethylene, propylene, amylene, butylene mostlys come from petroleum path, as catalytic cracking, steam are split
Solution etc..In recent years, domestic coal chemical industry is quickly grown, and coal-to-olefin, methanol-to-olefins project start one after another, greatly abundant
Domestic ethylene, propylene market.In the U.S., shale gas revolution not only makes gas production great outburst, and shale gas
The yield of associated gas such as ethane, propane also increases sharply, and ethane, propane can also produce ethylene, propylene with dehydrogenation.
The new Chemical Engineering Technology developed at present provides life all to produce ethylene, based on propylene, without new technical method
Produce butylene and amylene.Traditional butylene source includes refining plant C 4 and c4 cleavage, and refining plant C 4 comes from catalytic cracking unit (FCC), secondary
Production C4 amount is related with cracking level and catalyst, and alkene accounts for about the 52% of C4, based on 2- butylene and isobutene；C4 cleavage is stone
The co-product of petroleum hydrocarbon cracking ethylene preparation, C4 hydrocarbon yield is related with cracking stock and cracking severity, and olefin(e) centent accounts for the 93% of C4, with
Based on butadiene and isobutene.When using naphtha as cracking stock, C4 hydrocarbon yield is about the 40% of ethylene yield.1- butylene is to close
At sec-butyl alcohol, the raw material of dehydrogenation butadiene；Suitable, anti-2- butylene is for synthesizing C4, C5 derivative and producing crosslinking agent, overlapping vapour
Oil etc.；The purposes of isobutene is more extensive, not the still raw material of gasoline additive MTBE, be also used for manufacture butyl rubber, gather it is different
Butene rubber may also be fabricated which the polyisobutylene polymer of different molecular weight for use as lube oil additive, resin etc..Amylene is also
Important source material in fine chemistry industry.
For the status of domestic development of chemical industry, this patent develops one kind using methanol or dimethyl ether as raw material, utilizes circulation
The method that fluidized-bed reactor prepares alkene, especially C3, C4 and C5 alkene.
Summary of the invention
It is an object of the invention to solve problems of the prior art, a kind of utilization recirculating fluidized bed reaction work is provided
The method that skill prepares more carbon olefins by methanol.
To achieve the above object, the present invention provides a kind of using ciculation fluidized bed reaction technique by methanol or dimethyl ether
The method of standby olefin product, this method carry out in the reaction system for including fluidized-bed reactor and regenerator, using including first
The raw material of the mixture of alcohol, dimethyl ether or methanol and dimethyl ether, being equipped in a fluidized bed reactor includes that ZSM-5 molecular sieve is made
For the fluid catalyst of active component, so that the raw material is in the fluidized-bed reactor in the fluid catalyst
It is reacted under catalytic action, generates the product mix gas comprising olefin product, the olefin product includes propylene, butylene and penta
Alkene；
During the reaction, carbon distribution occurs for the fluid catalyst, at least one of the progress reaction
During point, process catalyst regeneration step as described below is carried out: so that at least part of the fluid catalyst of carbon distribution
It is transferred in the regenerator, at least part carbon distribution on catalyst is removed in the regenerator, then make described urge again
Agent returns in the fluidized-bed reactor.
According to embodiment of the present invention, the fluidized-bed reactor and regenerator respectively include a stripping section, vapour
Mention stripping fluid that section uses and be selected from vapor or inert media, the inert media can selected from nitrogen, helium, air or
Argon gas, the catalyst of carbon distribution are stripped in the stripping section in the fluidized-bed reactor before being transferred to regenerator,
Catalyst after regenerating in regenerator undergoes stripping first in the stripping section of regenerator, and it is anti-then to return the fluidized bed
It answers in device.
According to another implementation of the invention, on the basis of the weight of the catalyst in the fluidized-bed reactor
Meter starts to carry out the regeneration step when the amount of carbon distribution on the catalyst is 0.5-5 weight %.
It according to another implementation of the invention, is during the reaction with continuous after the regeneration step starts
Mode carry out, or carried out with the isolated period.
According to another implementation of the invention, the raw material optionally includes vapor, is steamed in the feed comprising water
In the case where gas, the vapor is greater than zero with the weight ratio of the methanol and/or dimethyl ether and is less than or equal to 0.3:1；Institute
The temperature stated when raw material enters the fluidized-bed reactor is 250-400 DEG C.
According to another implementation of the invention, the fluid catalyst is prepared by following steps:
(1) ZSM-5 molecular sieve, host material, binder and water are mixed, is configured to aqueous slurry, it is aqueous with this
It is counted on the basis of the total weight of slurries, wherein the total content of component in addition to water is 20-50 weight %；
(2) slurries made from step (1) are spray-dried, graininess intermediate product is made；
(3) graininess intermediate product made from step (2) is roasted, the fluid catalyst is made.
According to another implementation of the invention, on the basis of the total weight of the component in the slurries in addition to water
It counts, the content of ZSM-5 molecular sieve is 20-40 weight % in the slurries, and the silica alumina ratio of the ZSM-5 molecular sieve is preferred 200-
400, specific surface area 300-400m2/ g, Kong Rongwei 0.18-0.24cm3/ g, host material are one in kaolin or diatomite
Kind, mass content 20-50%, binder is silica solution, Aluminum sol, mixture one or more of in boehmite,
Its mass content is 10-40%.The meso-position radius of the fluid catalyst is 70-90 microns, with the total weight of the catalyst
On the basis of count, content < 0.5% of catalyst granules of the granularity less than 20 microns.
According to another implementation of the invention, the technological parameter of the fluidized-bed reactor are as follows: reaction temperature 450-
550 DEG C, the mass space velocity 4-10h of methanol/dimethyl ether-1, reactor pressure (gauge pressure) is 0.05-0.25MPa, the sky in reactor
Tower speed is 0.4-1.2m/s, is counted on the basis of the weight of the catalyst in the fluidized-bed reactor, when on the catalyst
When the amount of carbon distribution is 0.5-5 weight %, start to carry out the regeneration step.
According to another implementation of the invention, the regenerator is also fluidized bed.Another reality according to the present invention
Apply mode, the technological parameter of the regenerator are as follows: 350-450 DEG C of regeneration temperature, regenerating medium is air, regenerator pressure (table
Pressure) it is 0.05-0.25MPa, the superficial linear velocity in a column in regenerator is 0.1-0.6m/s.
According to another implementation of the invention, conversion ratio > 99.5% of methanol and/or dimethyl ether in the raw material,
Propylene content is 30-50 moles of % in product mix gas, and butene content is 20-30 moles of %, and the content of amylene is rubbed for 10-20
You are %, and the product mix gas also includes by-product selected from the following: C6+ hydro carbons, ethylene and alkane, the alkane include first
Alkane, ethane, propane, butane, pentane and hexane.
Carbon deposition catalyst may be implemented by the way that fluidized-bed reactor to be combined with the regenerator for being all fluidized bed in the present invention
Cyclic regeneration, while the selectivity of C3 and C4 alkene in product can be made to be significantly improved.In addition, present invention optimizes works
Skill condition improves the methanol/dimethyl ether air speed in reactor, reduces the water alcohol ratio in feed stream, while reducing again
Raw required temperature, energy consumption needed for thus greatly reducing regeneration.
Further illustrate the preferred embodiment of the present invention below by specific embodiment, but guarantor of the invention
Shield range is not limited only to this.Can by carrying out various changes or combination to the preferred embodiment of the present invention, without departing from
Under the premise of the protection scope that claims of the present invention limits, the other embodiments of the present invention are obtained, still can be realized
Similar technical effect.
Detailed description of the invention
Fig. 1 is the schematic diagram of fluidized-bed reactor and regenerator according to embodiment of the present invention.
Fig. 2 is the commerical test system flow chart of another embodiment according to the present invention, the production scale of the system
For 20,000 tons of methanol/years.
The each device and device numbering of system in Fig. 2 are as follows:
R1101- fluidized-bed reactor R1102- regenerator
V1101- methanol surge tank P1101A/B- methanol pump
The main wind-powered electricity generation heater of E1101, E1102, E1103- heat exchange of methanol device E1112, E1113-
T1201- quenching column T1202- water scrubber
V1114- surge tank V1115- oil water separator
E1106, E1107, E1108- heat exchanger
Specific embodiment
" range " disclosed herein is in the form of lower and upper limit.It can be respectively one or more lower limits and one
Or multiple upper limits.Given range is defined by a selected lower limit and a upper limit.Selected lower and upper limit limit
The boundary of special range is determined.All ranges that can be defined in this way comprising and can combine, i.e., any lower limit
It can combine to form a range with any upper limit.For example, the range of 60-120 and 80-110 are listed for special parameter, reason
Solution is that the range of 60-110 and 80-120 is also to expect.In addition, if the minimum zone value 1 and 2 listed, and if list
Maximum magnitude value 3,4 and 5, then below range can all expect: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, numberical range " a-b " indicates the contracting of any real combinings between a to b
Sketch form shows that wherein a and b is real number.Such as numberical range " 0-5 " expression has all listed between " 0-5 " herein
Whole real numbers, " 0-5 " are that the breviary of these combinations of values indicates.
If be not specifically stated, term used in this specification " two kinds " refers to " at least two ".
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and preferred implementation side
Formula can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can
New technical solution is formed to be combined with each other.
In the present invention, if without particularly illustrating, all steps mentioned in this article can be carried out sequentially, can also be with
It is random to carry out, it is preferred that being that sequence carries out.For example, indicating that the method can wrap the method includes the steps (a) and (b)
The step of sequence carries out (a) and (b) are included, also may include the step of sequence carries out (b) and (a).For example, described mention the side
Method may also include step (c), indicate that step (c) can be added to the method with random order, for example, the method may include
Step (a), (b) and (c) may also comprise step (a), (c) and (b), also may include step (c), (a) and (b) etc..
In the present invention, if without particularly illustrating, " comprising " mentioned in this article indicates open, is also possible to seal
Enclosed.For example, the " comprising " can indicate can also only can also to include the member listed comprising the other elements that do not list
Part.
The substantially composition and connection of each equipment are shown in equipment schematic diagram shown in the drawings of the invention
Connect relationship, in order to highlight, some of structures may have been carried out it is out-of-proportion zoom in or out, ruler shown in the drawings
Very little ratio can't be construed as limiting protection scope of the present invention.
In the present invention, " C1 " and " C1 hydro carbons " may be used interchangeably, and the hydro carbons containing a carbon atom be indicated, in this hair
In bright, methane is referred to.Similarly, " C2 " and " C2 hydro carbons " may be used interchangeably, and indicate the hydro carbons of the carbon atom containing there are two,
In the present invention, ethane, ethylene are generally referred to, acetylene is seldom related to；" C3 " and " C3 hydro carbons " may be used interchangeably, indicate containing
The hydro carbons of three carbon atoms generally refers to propylene, propane and its all kinds of isomers in the present invention；" C4 " and " C4 hydro carbons "
It may be used interchangeably, indicate the hydro carbons containing four carbon atom, in the present invention, generally refer to butylene, butane and its all kinds of
Isomers；" C5 " and " C5 hydro carbons " may be used interchangeably, and indicate containing there are five the hydro carbons of carbon atom, such as pentane, amylene and its different
Structure body；"C6+", " C6 or more " and " C6 or more hydro carbons " may be used interchangeably, indicate containing being greater than or equal to six carbon atoms
Hydro carbons.In addition, in the present invention, such as " certain alkene " expression upperseat concept of propylene, butylene, amylene, the institute including such alkene
There are isomeric forms, such as the various isomeries formed by carbon atom connection type or the difference of carbon-to-carbon double bond position
Body and cis-trans-isomer etc..Similar, " certain alkane " or " certain alkynes " includes similarly by carbon atom connection type or carbon-to-carbon
The differences of three key positions and the various isomers formed and steric isomer etc..
Fig. 1 shows the schematic diagram of the fluidized-bed reactor and regenerator that use according to embodiment of the present invention.
According to embodiment of the present invention, the regenerator is also a fluidized bed plant.Fluidized-bed reactor 1 from top to bottom according to
Secondary includes settling section 1c, conversion zone 1b and stripping section 1a three parts.Catalyst solid particle packing enters the conversion zone of the fluidized bed
In 1b, the raw material 3 comprising methanol and/or dimethyl ether and optional vapor is introduced into the reactor.Unstripped gas circulation
It crosses the solid layer of the catalyst solid particle and solid particle is made to be in suspended motion state, gas occurs in conversion zone 1b
Solid phase reaction or liquid and solid phase reaction.Product air-flow or liquid stream after reaction are separated off here up to settling section 1c
The catalyst solid particle carried under one's arms in product mixture, the solid particle return conversion zone 1b being then demultiplex out, and product mix
Object 7 leaves from the top of reactor 1.According to embodiment of the present invention, cyclonic separation is provided in the settling section 1c
Device, for collecting solid particle.
According to embodiment of the present invention, the lower part conversion zone 1b, which can be set, is distributed device.According to the present invention one
A embodiment, distributor be with being distributed in the plate of through-hole therein, the through-hole can according to need with specific pattern or
Person's random pattern is distributed in distributor, is used to so that material is evenly distributed in distributor.
With the progress of reaction, carbon distribution can be generated on catalyst granules, this will lead to being gradually reduced for catalyst activity.Root
According to an embodiment of the invention, when the carbon distribution of catalyst granules reaches specified level, by the valve of 1 bottom of reactor
Door is opened, so that the catalyst solid particle of carbon distribution is sent into regenerator 2 after by stripping section 1a.Why stripping is used
Section 1a is the oil gas in order to remove attachment removal from catalyst solid particle, such as C5, C5 and C6+ hydro carbons.In the stripping process,
From the bottom of stripping section, perhaps the position input stripping gas stripping gas on the lower side can be vapor or nitrogen
Gas.According to embodiment of the present invention, in the catalyst solid by being left from reactor bottom after the stripping section
All oil gas, such as C5, C5 and C6+ hydro carbons for adhering on particle etc. can be completely removed.
According to embodiment of the present invention, the temperature for inputting the raw material 3 of fluidized-bed reactor 1 is 250-400 DEG C, or
Person is within the scope of following any two numerical value is combined with each other and to be formed: 250,260,270,280,290,300,310,320,
330,340,350,360,370,380,390,400℃.Can be in the raw material pure methanol, pure dimethyl ether, methanol with
The mixture of dimethyl ether arbitrary proportion, or vapor can also be additionally comprised.It is described in the case where raw material includes vapor
The weight ratio of vapor and the methanol and/or dimethyl ether can be within the scope of following any two numerical value mutually forms:
0.005、0.008、0.01、0.02、0.05、0.08、0.1、0.12、0.15、0.16、0.17、0.18、0.19、0.20、0.21、
0.22、0.23、0.24、0.25、0.26、0.27、0.28、0.29、0.30。
According to another implementation of the invention, the reaction temperature in the reactor be 450-550 DEG C, or for
Lower any two numerical value is combined with each other to be formed within the scope of: 450,460,470,480,490,500,510,520,530,540,
550℃.According to another implementation of the invention, the mass space velocity of the raw material in the reactor is 4-10h-1, Huo Zhewei
Following any two numerical value is combined with each other to be formed within the scope of: 4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9,9.5,
10h-1.According to another implementation of the invention, the pressure (gauge pressure) in the reactor is 0.05- during the reaction
0.25MPa, or within the scope of being combined with each other and to be formed for following any two numerical value: 0.06,0.08,0.09,0.10,
0.12,0.15,0.16,0.17,0.18,0.19,0.20,0.21,0.22,0.23,0.24,0.25MPa.It is according to the present invention another
One embodiment, the superficial linear velocity in a column in the reactor are 0.4-1.2m/s, or are following any two numerical value mutually group
It closes within the scope of being formed: 0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2m/s.Another reality according to the present invention
Mode is applied, when the carbon distribution on the catalyst is greater than 0.5-5 weight %, starts the catalyst of carbon distribution being gradually transported to regeneration
The regeneration step is carried out in device.During being reacted, needs according to specific reaction condition, regeneration condition and urge
The cycle rate of catalyst is adjusted in carbon distribution speed in agent.According to embodiment of the present invention, the reaction
The every 1-20 hours circulation primary of catalyst in device.Circulation primary described herein is the circulation according to catalyst in a regenerator
Rate calculations, the quality of the catalyst by regeneration cycle are equal to the original quality for the catalyst being added in reactor, are not
Strictly referring to all catalyst feeds, all just circular regeneration is primary.
Solid particle catalyst used in reactor of the invention is comprising ZSM-5 molecular sieve consolidating as active component
Body catalyst particle.According to embodiment of the present invention, the catalyst can be by method comprising the following steps system
It is standby: (1) ZSM-5 molecular sieve, host material, binder and water to be mixed, are configured to aqueous slurry, with the aqueous slurry
It is counted on the basis of total weight, wherein the total content of component in addition to water is 20-50 weight %；(2) to step (1) slurry obtained
Liquid is spray-dried, and graininess intermediate product is made；(3) graininess intermediate product made from step (2) is roasted, is made
Obtain the fluid catalyst.According to another implementation of the invention, with the component in the slurries in addition to water
It is counted on the basis of total weight, the content of ZSM-5 molecular sieve is 20-40 weight %, the sial of the ZSM-5 molecular sieve in the slurries
Than for preferred 200-400, specific surface area 300-400m2/ g, Kong Rongwei 0.18-0.24cm3/ g, host material be kaolin or
One of diatomite, the mass content in the slurries is 20-50%, and binder is silica solution, Aluminum sol, intends thin water aluminium
One or more of mixture in stone, the mass content in the slurries are 10-40%.In the fluid catalyst
Position diameter is 70-90 microns, is counted on the basis of the total weight of the catalyst, the content of catalyst granules of the granularity less than 20 microns <
0.5%.In yet another embodiment of the present invention, the slurries also include pore creating material.Preferably, the pore creating material be selected from
One of lower substance is a variety of: sesbania powder, polyvinyl alcohol, methylcellulose, with the component in the slurries in addition to water
Total weight on the basis of count, the content of pore creating material described in the slurries is 0.01-1 weight %.Preferably implement at another
In mode, the slurries also include dispersing agent, and the dispersing agent is selected from one of following substance or a variety of: n-octyl alcohol, carbonic acid
Hydrogen ammonium, bicarbonate diammonium, are counted on the basis of the total weight of the component in the slurries in addition to water, dispersing agent in the slurries
Content be 0.01-1 weight %.In yet another embodiment of the present invention, in the step (2), atomizer is used
Drier or press spray drier are spray-dried, and the inlet temperature of spray dryer is 250-300 DEG C, outlet temperature
It is 150-200 DEG C, the feed rate that slurries input the spray dryer is 100-500ml/min；In the step (3),
400-600 DEG C, preferably 550 DEG C at a temperature of 3-6 hours, roasting in preferably 4 hours are carried out to the graininess intermediate product.
The host material of catalyst of the present invention is used to prepare as in kaolin, calcined kaolin, diatomite, boehmite, montmorillonite
It is one or more, there is partial size less than 2 microns.By using the host material, can play improve catalyst strength,
The effect of wearability.A degree of dehydration and/or decomposition may occur in roasting process for the host material, such as quasi-
Boehmite understands dehydration in roasting process and ultimately forms aluminium oxide, it is also possible to which dehydration does not occur for some host material
And/or it decomposes.In the present invention, all these components for including in product catalyst are referred to as " being originated from the host material
Component ".
Catalyst of the invention includes the component from the binder of 10-45 weight %, which is by binder
The remaining component after being spray-dried and being roasted.The binder can improve entire slurry system in slurry stage
Uniformity and fluid property, while being also beneficial to improve the overall mechanical strength of final catalyst obtained, it is resistance to significantly improve its
Mill property.According to specific needs, the composition of binder can be controlled by adjusting the type and content of binder.For this hair
Bright precursor is selected from one of following material or a variety of: alkaline silica sol, acidic silicasol, Aluminum sol, aluminum phosphate etc..Alkali
Property silica solution indicate the colloid that is formed in water of silica dioxide granule, the average grain diameter of the silica dioxide granule is that 8-20 is micro-
Rice, pH range are 9-10, and the molecular formula of silica contained therein can be denoted as SiO2·nH2O, with the gross weight of the silica solution
It counts on the basis of amount, calculates in the form of an oxide, wherein include the silica of 15-40 weight %, 0.2-0.4 weight %'s
Na2The water of O and surplus.(25 DEG C) of viscosity of the alkaline silica sol are 2-2.5MPaS, and (25 DEG C) of density are 1.1-1.3
Gram per centimeter3.Acidic silicasol is also known as hydrosol of silicic acid, is that polymeric silica particle is dispersed in water the acidity to be formed
Colloid, pH value 2-4 are counted on the basis of the total weight of the acidic silicasol, are calculated in the form of an oxide, wherein including
The silica of 30-31 weight %, less than the Na of 0.006 weight %2The water of O and surplus.The viscosity of the acidic silicasol
(25 DEG C) are less than 6MPaS, and (25 DEG C) of density are 1.19-1.21 gram per centimeter3, the average grain diameter of silica dioxide granule receives for 5-20
Rice can stablize holding three months without forming any precipitating under normal temperature conditions.Aluminum sol is alumina particle shape in water
At colloid, wherein solid concentration is 10-40 weight %, and pH value 1-3, the average grain diameter of alumina particle is 10-50 nanometers,
Wherein the chemical formula of alumina particle can write Al2O3·nH2O。
With continued reference to Fig. 1, regenerator 2 is also a fluidized bed plant, includes settling section 2c, conversion zone 2b under upper
With tri- parts stripping section 2a.Carry out the carbon deposition catalyst of autoreactor 1 after the stripping processing in stripping section 1a, conveys
Enter in the regenerator 2.In conversion zone 2b, the carbon distribution on catalyst surface is under the action of regeneration gas 4 (preferably air)
It is oxidized and removes, so that catalyst is regenerated.Air-flow in regenerator 2 carries out gas-particle separation operation in settling section 2c,
The solid particle wherein carried under one's arms is removed, then flue gas 8 is discharged above regenerator 2.Catalyst after regeneration is under regenerator
It is stripped in the stripping section 2a in portion, to remove CO, the CO that may carry on catalyst granules2And O2Equal gases, then from regeneration
The bottom of device 2 is transmitted back in reactor 1 along pipeline 6.It is defeated from the bottom of stripping section or position on the lower side in the stripping process
Enter stripping gas, the stripping gas can be vapor or nitrogen.
According to embodiment of the present invention, the temperature in the regenerator is 350-450 DEG C, or is following any
Two values are combined with each other to be formed within the scope of: 350,360,370,380,390,400,410,420,430,440,450 DEG C.
According to another implementation of the invention, the pressure (gauge pressure) in the regenerator is 0.05-0.25MPa, or is following
Any two numerical value is combined with each other to be formed within the scope of: 0.05,0.06,0.07,0.08,0.09,0.10,0.11,0.12,
0.13,0.14,0.15,0.16,0.17,0.18,0.19,0.20,0.21,0.22,0.23,0.24,0.25MPa.According to this hair
Bright another embodiment, the superficial linear velocity in a column in the regenerator are 0.1-0.6m/s, or are following any two numerical value
It is combined with each other within the scope of being formed: 0.1,0.2,0.3,0.4,0.5,0.6m/s.
According to embodiment of the present invention, before the reaction starts, in reactor 1, regenerator 2 and pipeline 5 and 6
In fresh solid catalyst has been loaded all in accordance with certain ratio.At the beginning of reacting progress, the valve on pipeline 5 and 6 is located
In closed state, the solid catalyst only in reactor 1 reacts at this time.With the progress of reaction, urging in reactor 1
Agent surface gradually has carbon distribution to be formed.The content for monitoring catalyst surface carbon distribution in real time by automation or artificial means, when urging
When agent area carbon content is more than specific threshold, the valve of pipeline 5 and 6 is opened, and regenerator 2 is made to bring into operation, from
And start the catalyst circulation between reactor and regenerator, a dynamic balance is thus maintained, by the carbon deposition quantity of catalyst
It is maintained at the level of 0.5-5 weight %.According to embodiment of the present invention, the carbon distribution level of catalyst is by with lower section
What formula carried out: taking out the sample of solid particle from reactor 1 according to specific time interval, carbon distribution is completely removed by heating
The poor re-computation carbon distribution ratio of front and back.
The schematic diagram that most simplified reactor and regenerator endless form are only shown in Fig. 1 of the invention, according to need
Want, can in addition add any one or more other device wherein, for example, feedstock device, raw material preprocessing device,
Heater, cooler, heat exchanger, material distribution device, entrance and exit of various materials etc..Furthermore it is also possible to as needed
Addition the substances such as product, by-product, catalyst are recycled, are separated, are purified, are burnt, waste processing etc. operations it is any its
Its device.
Fig. 2 is shown according to embodiment of the present invention, in figure other than using fluidized bed and regenerator, goes back volume
It is outer to have used numerous pretreatments and product separation system.As shown in Fig. 2, methanol feedstock enters methanol surge tank V1101, pass through pump
Methanol feedstock is transported to reactor R1101 by P1101A/B, methanol before entering the reactor, pass sequentially through 3 heat exchanger E1101,
E1102, E1103 heating, vapor are mixed with methanol into reactor before methanol enters reactor, this strand of gaseous mixture
Temperature be 250-370 DEG C, methanol reacts under the effect of the catalyst in reactor and generates product gas, product gas master
Forming is more carbon olefins and water, is introduced into after cyclone separator and the catalyst separation that product gas passes through reactor head
E1102 and material benzenemethanol heat exchange, then enter back into crude separation system.Catalyst warp with carbon distribution to a certain degree after reaction
It is flowed out after steam or nitrogen stripping from reactor bottom, is delivered to regenerator regeneration by conveying wind, the catalyst after regeneration
Being delivered to reactor again after stripping, the reaction was continued.After product gas enters crude separation system, it is introduced into quenching column T1201, then
Into water scrubber T1202, from water scrubber at the top of the product that comes out mainly organize the lighter hydrocarbons as C1-C5, this part lighter hydrocarbons can be into
The further later separation of row operates to obtain the products such as required C2-C5 alkene.According to another implementation of the invention, if
The main purpose of reaction is to obtain heavy hydrocarbon, the C1-C5 lighter hydrocarbons can also be sent to torch burning.From water scrubber bottom and swash
The product that cold tower bottom comes out mainly is organized as water and C5, C6+ heavy hydrocarbon, this partial material removes surge tank V1114, then removes grease again
Separator V1115 separation water outlet and heavy hydrocarbons.
Embodiment shown in Fig. 2 only lists a kind of specific embodiment of the invention, and the present invention is not limited thereto.
It can be according to specifically needing to obtain required olefinic product using various product postprocessings and lock out operation.
The present invention is designed by process described above, is optimized process conditions, is improved material benzenemethanol/dimethyl ether sky
Speed reduces the water alcohol ratio of raw material, reduces regeneration temperature range, can carry out the regeneration of catalyst at a lower temperature,
Greatly reduce regeneration energy consumption.
It has been found that when material benzenemethanol/dimethyl ether air speed is when 4-10 is small-1In the range of when, may be implemented
The feed stock conversion and selectivity of product of optimization.Below in an example with the comparison between inventive embodiments and comparative example
Demonstrate this point.
Reaction of the invention is carried out under the conditions of lower raw water alcohol ratio, and the water alcohol ratio in raw material is preferably no greater than
0.3.By reducing the moisture content in raw material, energy consumption of reaction can be significantly reduced, in addition technique of the invention may be implemented pair
The significant saving of water resource, this is also considerably advantageous from the point of view of environmental angle.
In addition, the regeneration of catalyst can be realized at a lower temperature in reaction system of the invention, it is thus significant to drop
It is low regenerate brought by energy consumption.In the prior art, the regeneration temperature of general recirculating fluidized bed is higher than 500 DEG C, and conventional
Regeneration temperature used by MTO equipment is above 600 DEG C.
Further illustrate the preferred embodiment of the present invention below by specific embodiment, but guarantor of the invention
Shield range is not limited only to this.Can by carrying out various changes or combination to the preferred embodiment of the present invention, without departing from
Under the premise of the protection scope that claims of the present invention limits, the other embodiments of the present invention are obtained, still can be realized
Similar technical effect.
Embodiment
Catalyst Preparation Example
Addition 600g ZSM-5 catalyst fines (silica alumina ratio 300), 1200g alkalinity silicon are molten in stainless steel cauldron
Glue, 600g kaolin, 400g boehmite, 2g sesbania powder, 1g n-octyl alcohol, 4000g deionized water, stir obtained
Aqueous slurry is spray-dried using atomizer drier, and the inlet temperature of the atomizer drier is 300
DEG C, outlet temperature is 180 DEG C, and the charging rate of slurries is 100ml/min, and spraying resulting pellet type catalyst intermediate product exists
2h is roasted under conditions of 650 DEG C, air atmosphere in Muffle furnace, obtains catalyst product.Use Beckman laser particle size analysis
The average grain diameter that instrument measures the catalyst microspheres is 81 microns.It repeats the above process, it is desired amount of that following experiment is made
Catalyst can scale up the additional amount of each component during preparing aqueous slurry to be contained more on a large scale
Aqueous slurry.
Embodiment 1
By 3 tons of Catalyst packings made above in the system into Fig. 2, wherein catalyst is 1t in reactor R1101,
Catalyst 1.5t in regenerator R1102, remaining 0.5t catalyst is in delivery pipe and other pipelines, urging in the close phase section of reactor
Agent weight is 0.35t.
Methanol is passed into fluidized-bed reactor R1101, methanol by being mixed into reactor after heat exchanger with water
Flow be 2500kg/h, methanol quality air speed be 7.14h-1, vapor flow is 250kg/h, the charging temperature of raw material in raw material
Degree is 350 DEG C, reactor pressure 0.12MPa, 520 DEG C of temperature.Reaction starts catalyst in reactor and regeneration at the beginning
Circulation between device.Regenerator pressure is 0.11MPa, and regeneration air quantity is 400m3/ h, oxygen content is 21% in regeneration gas, then
Linear velocity in raw device is 0.25m/s, and regenerator temperature is 360 DEG C.Internal circulating load of the catalyst between reactor and regenerator
For 1.5t/h.
The catalyst of regenerated catalyst with this condition, regenerator and reactor keeps stablizing, the catalysis in reactor
Agent carbon distribution content is 1.0-1.2%, and the catalyst carbon deposition in regenerator is 0.4-0.6%.
The analysis of reaction product is analyzed using on-line chromatograph, methanol conversion 99.79%, product composition are as follows: methane
0.9%, ethylene 5.60%, ethane 0.12%, propylene 39.09%, propane 1.04%, butylene 23.10%, butane 2.15%, penta
Alkene is 13.20%, pentane 1.87%, C6+ hydro carbons 12.85%, and isobutene content in butylene is 53.23%.
Embodiment 2
By 3 tons of Catalyst packings made above in the system into Fig. 2, wherein catalyst is 1t in reactor R1101,
Catalyst 1.5t in regenerator R1102, remaining 0.5t catalyst is in delivery pipe and other pipelines, urging in the close phase section of reactor
Agent weight is 0.3t.
Methanol is passed into fluidized-bed reactor R1101, methanol by being mixed into reactor after heat exchanger with water
Flow be 2600kg/h, methanol quality air speed be 8.67h-1, vapor flow is 200kg/h, the charging temperature of raw material in raw material
Degree is 300 DEG C, reactor pressure 0.105MPa, 530 DEG C of temperature.Reaction starts catalyst in reactor and regeneration at the beginning
Circulation between device.Regenerator pressure is 0.10MPa, and regeneration air quantity is 300m3/h, and oxygen content is 15% in regeneration gas, then
Linear velocity in raw device is 0.19m/s, and regenerator temperature is 400 DEG C.Internal circulating load of the catalyst between reactor and regenerator
For 1.5t/h.
The catalyst of regenerated catalyst with this condition, regenerator and reactor keeps stablizing, the catalysis in reactor
Agent carbon distribution content is 0.9-1.1%, and the catalyst carbon deposition in regenerator is 0.4-0.6%.
The analysis of reaction product is analyzed using on-line chromatograph, methanol conversion 99.89%, product composition are as follows: methane
1.36%, ethylene 6.59%, ethane 0.18%, propylene 40.59%, propane 1.00%, butylene 22.84%, butane 1.65%, penta
Alkene is 12.89%, pentane 1.55%, C6+ hydro carbons 11.03%, and isobutene content in butylene is 49.13%.
Embodiment 3
By 3 tons of Catalyst packings made above in the system into Fig. 2, wherein catalyst is 1t in reactor R1101,
Catalyst 1.5t in regenerator R1102, remaining 0.5t catalyst is in delivery pipe and other pipelines, urging in the close phase section of reactor
Agent weight is 0.4t.
Methanol is passed into fluidized-bed reactor R1101, methanol by being mixed into reactor after heat exchanger with water
Flow be 2500kg/h, methanol quality air speed be 6.25h-1, vapor flow is 100kg/h, the charging temperature of raw material in raw material
Degree is 250 DEG C, reactor pressure 0.105MPa, 510 DEG C of temperature.Reaction starts catalyst in reactor and regeneration at the beginning
Circulation between device.Regenerator pressure is 0.10MPa, and regeneration air quantity is 300m3/ h, oxygen content is 21% in regeneration gas, then
Linear velocity in raw device is 0.19m/s, and regenerator temperature is 380 DEG C.Internal circulating load of the catalyst between reactor and regenerator
For 1.5t/h.
The catalyst of regenerated catalyst with this condition, regenerator and reactor keeps stablizing, the catalysis in reactor
Agent carbon distribution content is 0.9-1.1%, and the catalyst carbon deposition in regenerator is 0.5-0.7%.
The analysis of reaction product is analyzed using on-line chromatograph, methanol conversion 99.95%, product composition are as follows: methane
1.42%, ethylene 6.03%, ethane 0.20%, propylene 43.23%, propane 1.41%, butylene 24.75%, butane 2.45%, penta
Alkene is 10.64%, pentane 1.73%, C6+ hydro carbons 8.14%, and isobutene content in butylene is 51.23%.
Comparative example 1
In order to investigate influence of the specific air speed of methanol feedstock to selectivity of product, applicant carried out this comparative examples 1
Experiment.In the comparative example, the step of embodiment described above 1 is repeated, difference is only that in the comparative example 1, by first
Alcohol mass space velocity sets 3.61h-1。
The analysis of reaction product is analyzed using on-line chromatograph, methanol conversion 99.91%, product composition are as follows: methane
1.4%, ethylene 11.60%, ethane 1.12%, propylene 36.09%, propane 2.04%, butylene 21.20%, butane 3.85%, penta
Alkene is 11.20%, pentane 2.37%, C6+ hydro carbons 9.13%, and isobutene content in butylene is 36.34%.
Comparative example 2
Also for influence of the specific air speed to feed stock conversion and selectivity of product for investigating methanol feedstock, applicant
The experiment of this comparative example 2 is carried out.In the comparative example, the step of embodiment described above 1 is repeated, difference is only that
In the comparative example 2, methanol quality air speed is set into 11.03h-1。
The analysis of reaction product is analyzed using on-line chromatograph, methanol conversion 95.61%, product composition are as follows: methane
0.7%, ethylene 5.32%, ethane 0.23%, propylene 38.19%, propane 1.54%, butylene 22.10%, butane 3.85%, penta
Alkene is 14.20%, pentane 1.37%, C6+ hydro carbons 12.5%, and isobutene content in butylene is 47.14%.
Claims (10)
1. a kind of method for preparing olefin product, this method in the reaction system for including fluidized-bed reactor and regenerator into
Row, using the raw material comprising methanol, dimethyl ether or methanol and the mixture of dimethyl ether, in a fluidized bed reactor equipped with comprising
Fluid catalyst of the ZSM-5 molecular sieve as active component, so that the raw material is in the fluidized-bed reactor described
It is reacted under the catalytic action of fluid catalyst, generates the product mix gas comprising olefin product, the olefin product packet
Containing propylene, butylene and amylene；
During the reaction, carbon distribution occurs for the fluid catalyst, at least part mistake for carrying out the reaction
Cheng Zhong carries out process catalyst regeneration step as described below: so that at least part of the fluid catalyst of carbon distribution shifts
Into the regenerator, at least part carbon distribution on catalyst is removed in the regenerator, then makes the catalyst again
It returns in the fluidized-bed reactor.
2. the method as described in claim 1, which is characterized in that the fluidized-bed reactor and regenerator respectively include one and strip
Section, the stripping fluid that stripping section uses are selected from vapor, nitrogen, helium, air, argon gas, and the catalyst of carbon distribution is being transferred to again
It is stripped in the stripping section in the fluidized-bed reactor before raw device, the catalyst after regenerating in a regenerator is first
Stripping is undergone in the stripping section of regenerator, is then returned in the fluidized-bed reactor.
3. the method as described in claim 1, which is characterized in that using the weight of the catalyst in the fluidized-bed reactor as base
Quasi- meter starts to carry out the regeneration step when the amount of carbon distribution on the catalyst is 0.5-5 weight %.
4. the method as described in claim 1, which is characterized in that after the regeneration step starts, be during the reaction with
What continuous mode carried out, or carried out with the isolated period.
5. the method as described in claim 1, which is characterized in that the raw material optionally includes vapor, includes in the feed
In the case where vapor, the vapor is greater than zero with the weight ratio of the methanol and/or dimethyl ether and is less than or equal to 0.3:
1；The temperature when raw material enters the fluidized-bed reactor is 250-400 DEG C.
6. the method as described in claim 1, which is characterized in that the fluid catalyst is prepared by following steps:
(1) ZSM-5 molecular sieve, host material, binder and water are mixed, is configured to aqueous slurry, with the aqueous slurry
Total weight on the basis of count, wherein the total content of component in addition to water be 20-50 weight %；
(2) slurries made from step (1) are spray-dried, graininess intermediate product is made；
(3) graininess intermediate product made from step (2) is roasted, the fluid catalyst is made.
7. method as claimed in claim 6, which is characterized in that the total weight with the component in the slurries in addition to water is
Benchmark meter, the content of ZSM-5 molecular sieve are 20-40 weight %, and the silica alumina ratio of the ZSM-5 molecular sieve is preferred 200-400, than
Surface area is 300-400m2/ g, Kong Rongwei 0.18-0.24cm3/ g, host material are one of kaolin or diatomite, matter
Amount content is 20-50%, and binder is silica solution, Aluminum sol, mixture one or more of in boehmite, and quality contains
Amount is 10-40%.The meso-position radius of the fluid catalyst is 70-90 microns, is counted on the basis of the total weight of the catalyst,
Content < 0.5% of catalyst granules of the granularity less than 20 microns.
8. the method as described in claim 1, which is characterized in that the technological parameter of the fluidized-bed reactor are as follows: reaction temperature
450-550 DEG C, the mass space velocity 4-10h of methanol/dimethyl ether-1, reactor pressure (gauge pressure) is 0.05-0.25MPa, in reactor
Superficial linear velocity in a column be 0.4-1.2m/s, counted on the basis of the weight of the catalyst in the fluidized-bed reactor, when the catalysis
When the amount of carbon distribution is 0.5-5 weight % in agent, start to carry out the regeneration step.
9. the method as described in claim 1, which is characterized in that the technological parameter of the regenerator are as follows: regeneration temperature 350-450
DEG C, regenerating medium is air, and regenerator pressure (gauge pressure) is 0.05-0.25MPa, and the superficial linear velocity in a column in regenerator is 0.1-
0.6m/s。
10. the method as described in claim 1, which is characterized in that the conversion ratio of methanol and/or dimethyl ether in the raw material >
99.5%, propylene content is 30-50 moles of % in product mix gas, and butene content is 20-30 moles of %, and the content of amylene is
10-20 moles of %, the product mix gas also include by-product selected from the following: C6+ hydro carbons, ethylene and alkane, the alkane
Including methane, ethane, propane, butane, pentane and hexane.
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| CN114133309A (en) * | 2021-11-23 | 2022-03-04 | 北京惠尔三吉绿色化学科技有限公司 | Method for preparing low-carbon olefin from methanol |
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