CN105478162B - Reduce the catalyst of green coke low-carbon olefines high-output - Google Patents
Reduce the catalyst of green coke low-carbon olefines high-output Download PDFInfo
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Abstract
Reduce the catalyst of green coke low-carbon olefines high-output, including 10-85 weight % al binder, the clay of 15-60 weight % molecular sieve and 0-75 weight %, the molecular sieve is MFI structure zeolite or MFI structure zeolite and y-type zeolite, the preparation method of the catalyst is the following steps are included: form slurries for al binder, clay, molecular sieve, water and carboxymethyl cellulose, spray drying optionally roasts.Catalyst spherical degree provided by the invention is high, and productivity of low carbon olefin hydrocarbon is high, and coke yield is low.
Description
Technical field
The present invention relates to a kind of catalyst of heavy oil fluidized producing low-carbon alkene by catalytic pyrolysis and its preparations and application.
Background technique
Low-carbon alkene (ethylene and propylene) is important industrial chemicals, and demand is very vigorous and constantly increases.At present
Ethylene, the propylene in 95% or more market are provided by naphtha steam cracking and heavy-oil catalytic preparing low-carbon olefins technology.In recent years,
It is deteriorated again as petroleum gradually becomes, heavy-oil catalytic preparing low-carbon olefins technology is because low energy consumption, ingredient requirement is low, product distribution
Flexible adjustment obtains large development, has bigger development prospect on meeting future market increasing need.
CN1093101A (Chinese ZL93102783.7) discloses a kind of for producing the catalyst for cracking of low-carbon alkene, is
It is made of the clay, the inorganic oxide of 5-99% and the zeolite of 1-50% of 0-70% (being counted on the basis of catalyst weight).Its
In zeolite be 0-25 weight % REY or Y-type high-Si zeolite and 75-100 weight % phosphorous and rare earth five-membered ring silica-rich zeolite
Mixture.The catalyst have compared with using HZSM-5 zeolite as the higher hydrothermal activity stability of the catalyst of active component, turn
Rate and C2 =-C4 =Yield.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new heavy oil catalytic pyrolysis containing al binder and molecular sieve
The catalyst and preparation method thereof of low-carbon alkene is produced, which has better sphericity.
The present invention provides a kind of catalyst of producing low-carbon alkene by catalytic pyrolysis, which includes the 10-85 in terms of butt
Weight % al binder, the clay of the weight % molecular sieve of the 15-60 in terms of butt and the weight of the 0-75 in terms of butt %, the molecular sieve
For MFI structure zeolite or MFI structure zeolite and y-type zeolite；The preparation method of the catalyst is the following steps are included: aluminium is bonded
Agent, clay, molecular sieve, water and carboxymethyl cellulose form slurries, will be formed by slurries spray drying forming, optionally roast
It burns.
The present invention also provides a kind of method of producing low-carbon alkene by catalytic pyrolysis, it is included in hydrocarbon under conditions of catalytic pyrolysis
Oily the step of being contacted with catalytic cracking catalyst provided by the invention.
Catalyst provided by the invention has lower coke yield, low-carbon with higher for heavy oil catalytic pyrolysis
Olefins yield.Catalyst of the present invention can be used as auxiliary agent or catalyst for hydrocarbon oil catalytic cracking, be particularly suited for heavy oil fluidized catalysis
Cracking.The preparation method of catalyst provided by the invention, is added carboxymethyl cellulose during the preparation process, can be with al binder
So that catalyst spherical degree is good, wear-resisting property is good for collocation well, improves pore volume and increases specific surface area, while can improve
Product distribution；It can be used for preparing macropore carrier Cracking catalyst.Heavy oil catalytic pyrolysis production low-carbon alkene provided by the invention
Method can be used for fluid catalytic cracking of heavy oil production low-carbon alkene, especially production propylene.The heavy oil such as normal pressure gas
One of oil, vacuum gas oil (VGO), reduced crude, decompression residuum are a variety of.
Specific embodiment
The catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention, preparation process include by al binder, glue
Soil, molecular sieve and water are mixed with beating, wherein are additionally added carboxymethyl cellulose during being mixed with beating, the slurries that then will be obtained
Spray drying.Wherein the dry weight ratio of al binder, molecular sieve and clay is 10-85:15-60:0-75；Carboxymethyl cellulose
Weight ratio with the al binder in terms of butt is 2-40:100.The dry weight is that 800 DEG C of raw material roastings obtain for 1 hour
The weight of the solid product arrived.
The catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention includes the weight % aluminium of the 10-85 in terms of butt bonding
Agent, the clay of the weight % molecular sieve of the 15-60 in terms of butt and the weight of the 0-75 in terms of butt %, the content of the clay are preferably
15-60 weight %.Under preferable case, the catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention includes in terms of butt
10-55 weight % al binder, the clay of the weight % molecular sieve of the 15-55 in terms of butt and the weight of the 10-55 in terms of butt %；Example
Such as, the catalyst is made of the clay of 15-50 weight % al binder, 15-50 weight % molecular sieve and 20-50 weight %,
The molecular sieve is MFI structure zeolite or MFI structure zeolite and y-type zeolite.
The catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention, in preparation process, al binder, clay,
The solid content for the slurries that molecular sieve, water and carboxymethyl cellulose are formed is preferably 5-45 weight %, more preferably 10-35 weight
Measure %.The solid content is the percentage for roasting 1 hour obtained solid products weight and slurry weight after slurries are dry in 800 DEG C
Than.
Preferably, in the catalyst, the content of clay is preferably 15-60 weight %.It is described by al binder, it is viscous
It is as follows that soil, molecular sieve and carboxymethyl cellulose form slurry method: clay, carboxymethyl cellulose and water are formed into slurries, it will
Obtained slurries are mixed with beating with molecular sieve, are then mixed with binder.Preferably, it is described by clay, carboxymethyl cellulose with
It is as follows that water forms slurry method: clay and water being mixed with beating, it is water-soluble that carboxymethyl cellulose is added during being beaten stirring
Liquid, carboxymethyl cellulose weight account for the 3-30 weight that kaolin, carboxymethyl cellulose weight and water are beaten the slurry weight to be formed
Measure %, preferably 3-10 weight %；Then, it stirs 10-20 minutes, stops stirring, stand 10-20 minutes, be stirred for 10-20 points
Clock stops stirring, stands 10-20 minutes, is stirred for 10-20 minutes, whole process slurry temperature is maintained at 60 DEG C or less for example
It is 15-60 DEG C, 15-50 DEG C or 20-40 DEG C.There is the catalyst obtained in this way carboxymethyl cellulose to be evenly distributed, catalyst is low
Olefin yield is high, the effect that wear-resisting property is good, coke yield is low.Carboxymethyl cellulose in the carboxymethyl cellulose aqueous solution
Concentration be 2-20 weight % be, for example, 5-15 weight %.Clay in the slurries that wherein clay, water and carboxymethyl cellulose are formed
Content be preferably 5-40 weight % be, for example, 5~25 weight %.
It is further preferred that it is as follows that al binder, clay, molecular sieve and carboxymethyl cellulose are formed slurry method: by clay
It being beaten with water, the carboxymethyl cellulose aqueous solution that concentration is 2-20 weight % is added, mashing stirring 10-20 minutes stops stirring,
10-20 minutes are stood, is stirred for 10-20 minutes, stirring is stopped, 10-20 minutes is stood, is stirred for 10-20 minutes, whole process
It is, for example, 0-60 DEG C that slurry temperature, which is maintained at 60 DEG C or less, is then mixed with beating with molecular sieve pulp, finally starches with al binder
Liquid mixing obtains the slurries that clay content is 5-40 weight % such as 5~25 weight %.The slurries obtained in this way are by spraying dry
After dry, the sphericity of the microballoon of obtained catalyst is more preferable；With better choice.
Catalyst spherical degree provided by the invention is preferable.In the present invention, sphericity (indicates) that measurement method is as follows with Φ:
The π of Φ=4 A/P2
In formula, Φ is sphericity (also referred to as degree of rounding of grains), and A is the projected area of particle, and P is particle projection perimeter.
The catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention, the clay are in clay commonly used in the art
One or more, for example, kaolin, rectorite, montmorillonite, diatomite, galapectite, saponite, sepiolite, attapulgite, water
One or more of talcum and bentonite.In the clay, metal impurities such as Fe, Ca, Mg etc., impurity member in clay of the present invention
Plain weight content is preferred are as follows: Fe2O3< 0.8%, CaO < 0.2%, MgO < 0.5%.
In the catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the present invention, the al binder be selected from aluminium oxide and
One or more of its precursor, the al binder content in terms of aluminium oxide are preferably 5-80 weight %.It is preferred that oxidation
Aluminium and its precursor are Aluminum sol, phosphorus Aluminum sol, aluminium containing salt (such as the sulfate of various aluminates, aluminium, nitrate, halogenation
Object), gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, the hydrated alumina with structure of similar to thin diaspore, have
Hydrated alumina, the hydrated alumina with gibbsite structure and the hydration with boehmite structure of one diaspore structure
One or more of aluminium oxide；The more excellent al binder is boehmite, or for boehmite and is selected from aluminium oxide
With the mixture of one or more of other precursors of aluminium oxide.Under preferable case, the al binder includes intending thin water
When aluminium stone, al binder, clay, molecular sieve, water and carboxymethyl cellulose are formed in slurry processes, the boehmite
Acidification pseudo-boehmite slurries first are formed with water and inorganic acid, are then bonded again with clay, molecular sieve, optional other aluminium
Agent, water and carboxymethyl cellulose form slurries；The boehmite and water and inorganic acid form acidification pseudo-boehmite
Slurries, the slurry solid content are preferably 5-40 weight %, and pH value is preferably 2-5 such as 3-4；In general, inorganic acid with aluminium oxide
The molar ratio of the boehmite of meter is that 0.15-0.35 for example can be 0.15-0.25:1；The inorganic acid such as hydrochloric acid,
One of nitric acid, sulfuric acid are a variety of.
The catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention, containing molecular sieve, the molecular sieve is described
Molecular sieve is MFI structure zeolite or MFI structure zeolite and y-type zeolite.The MFI structure zeolite is for example: ZSM-5 zeolite, ZSP
One of zeolite, ZRP zeolite are a variety of, the Y zeolite such as REY zeolite, HY zeolite, REHY zeolite；DASY zeolite,
One of USY zeolite is a variety of.With or without rare earth in the DASY zeolite, contain or P Modification component, for example,
DASY0.0,DASY1.0,DASY2.0；The USY zeolite contains or P Modification component with or without rare earth, for example, USY-1,
USY-2.During other components used in molecular sieve and catalyst preparation process are mixed with beating, it can first be prepared into solid content
For the molecular sieve pulp of 30-45 weight %, molecular sieve dry powder can also be added.Under preferable case, it is with catalyst dry weight
Benchmark, it is 0-45 weight %, MFI knot that the content of MFI structure zeolite, which is the content of 15-60 weight %Y zeolite, in the catalyst
Structure zeolite and y-type zeolite weight ratio can be, for example, 100:1-50 for 100:0-50；In the MFI structure zeolite silica with
The molar ratio of aluminium oxide is preferably 15-300:1.
There is the catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention conventional fluid catalytic cracking (FCC) to urge
The size distribution of agent, such as its average grain diameter (diameter) are 60-80 microns, and partial size (diameter) is 0-149 microns of (particle diameters
Greater than 0 and be no more than 149 microns) not low 90% volume of particle, partial size is 0-40 micron (particle diameter is greater than 0 and being no more than
40 microns) particle be no more than 20% volume.
The spray drying forming, can refer to existing method, and the present invention repeats no more.
The step of catalytic cracking catalyst provided by the invention, preparation method may also include roasting.Roasting condition is to urge
Usual roasting condition in fluidized cracking catalysts preparation process, but the temperature roasted is, for example, 300-800 DEG C not less than 300 DEG C,
Usually 350-650 DEG C, calcining time is preferably 1-6 hours.
In catalytic cracking method of the present invention, the condition that catalyst is contacted with hydrocarbon ils is the prior art, such as
Reaction temperature is 400 DEG C -750 DEG C.According to catalyst cracking method of the present invention, contain MFI structure in used catalyst
Zeolite, preferable reaction temperature are 480 DEG C -560 DEG C, introduce water vapour, the weight ratio of vapor and feedstock oil in reaction process
For 0.7-14:1.
Catalytic cracking method of the present invention contains catalyst provided by the invention in the catalyst, can also contain
Other Cracking catalyst.For example, when in catalyst provided by the present invention containing the zeolite with MFI structure, institute of the present invention
The catalyst of offer can be used alone, or after mixing as auxiliary agent with other Cracking catalyst, for producing low-carbon alkene；As
When auxiliary agent, on the basis of the total weight of catalyst, the content of catalyst provided by the invention is -30 weight % of 1 weight, preferably
- 30 weight % of 5 weight.The low-carbon alkene is butylene, propylene and ethylene.
Following example will be further described the present invention, but not thereby limiting the invention.
In each example and comparative example, Na in zeolite2O、Fe2O3、NiO、A12O3、SiO2Content surveyed with x-ray fluorescence method
Determine [referring to " petrochemical analysis method (RIPP experimental method), Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes].
It is surveyed in embodiment and comparative example using the CamsizerXT dynamic digital imaging particle analyzer of Lai Chi company, Germany
Try the sphericity of catalytic cracking catalyst.It in embodiment, is measured using dry method, determination condition are as follows: sample F.F. in feed well
Rate is 60% of maximum vibration rate as defined in instrument, and the rate that sample enters measurement window is maximum vibration as defined in instrument
The 55% of rate, sample introduction 1.2g.It uses the two-dimensional projection image of digital camera shooting particle, with digital picture
Processing software obtains the projected area and projection perimeter of particle, so that it may calculate the circularity of particle；Particle in sample is carried out
A large amount of roundness calculations take its statistical result (average value) to obtain the sphericity of sample.
Embodiment 1
By 19Kg halloysite (Suzhou china clay company industrial products, 72.3 weight % of solid content, through analysing impurity weight
Content is Fe2O3=0.76%, CaO are not detected, and MgO is not detected) plus 30Kg decationized Y sieve water, it is added after being beaten 30 minutes
Cmc soln 98Kg (aqueous solutions of 15 weight %), mashing stirring 20 minutes, stops stirring, stands 15 minutes, then
Stirring 20 minutes stops stirring, stands 15 minutes, is stirred for 20 minutes, obtains slurries A.Whole process slurry temperature is maintained at
15-40℃；Wherein the content of carboxymethyl cellulose is 10 weight % in slurries, and kaolinic content is 9.34 weight %；
20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, 63 weight % of solid content) is mixed
It closes, mashing, adjusting its pH value with hydrochloric acid (30 weight % of concentration, similarly hereinafter) is 3；10Kg Aluminum sol (Qilu Petrochemical catalyst is added
Factory produces, A12O3Content is 21.7 weight %), it stirs 40 minutes, obtains al binder slurries B, pH value 2.7；Slurries are solid
Content is 21.2 weight %
Molecular sieve pulp 20Kg (the wherein 8Kg of zeolite containing ZRP, ZRP Zeolite (SiO is added in slurries A2/Al2O3It rubs
That ratio) 40, phosphorous 2.5 weight the %, (RE containing rare earth2O3) 1 weight %, it is asphalt in Shenli Refinery, Sinopec catalyst Co., Ltd
Product), stir to get slurries C.
Slurries C is mixed with slurries B, is stirred 30 minutes, obtains 14.5 weight % slurries of solid content, and spray drying obtains
Grain A, 500 DEG C roast 4 hours, then wash away free Na ion, dry, obtain catalyst CA1.CA1 composition: kaolin 45.5%
Weight, 28 weight % of aluminium oxide, 26.5 weight % of molecular sieve.
Embodiment 2
According to the method for embodiment 1, unlike, the mashing repeatedly is not carried out in slurries A preparation process and is stopped
Only process.
By 19Kg halloysite (Suzhou china clay company industrial products, ibid) plus 30Kg decationized Y sieve water, it is beaten 30 points
Cmc soln 98Kg (15% aqueous solution) is added after clock, is beaten 60 minutes, obtains slurries A, whole process slurries
Temperature is maintained at 15-40 DEG C.
20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, 63 weight % of solid content) is mixed
It closes, mashing, adjusting its pH value with hydrochloric acid (30 weight % of concentration, similarly hereinafter) is 3；10Kg Aluminum sol (Qilu Petrochemical catalyst is added
Factory produces, A12O3Content is 21.7 weight %), it stirs 40 minutes, obtains al binder slurries B, pH value 2.7；
Molecular sieve pulp 20Kg (the wherein 8Kg of zeolite containing ZRP, ZRP Zeolite 40, phosphorous 2.5 weight are added in slurries A
Measure the %, (RE containing rare earth2O3) 1 weight %, it is middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery product), stir to get slurries C.
Slurries C is mixed with slurries B, is stirred 30 minutes, spray drying, obtains particle A, and 500 DEG C roast 4 hours, is then washed
Free Na ion is removed, it is dry, obtain catalyst CA2.
Embodiment 3
By 19Kg halloysite, (Maoming Kaolin, 75.4 weight % of solid content are Fe through analysing impurity content2O3=
0.76 weight %, CaO=0.32 weight %, MgO=0.25 weight %) plus 30Kg decationized Y sieve water, it is added after being beaten 30 minutes
Cmc soln 98Kg (aqueous solutions of 15 weight %), mashing stirring 20 minutes, stops stirring, stands 15 minutes, then
Stirring 20 minutes stops stirring, stands 15 minutes, is stirred for 20 minutes, obtains slurries A.Whole process slurry temperature is maintained at
60 DEG C or less.
20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, 63 weight % of solid content) is mixed
It closes, mashing, adjusting its pH value with hydrochloric acid (30 weight % of concentration, similarly hereinafter) is 3；10Kg Aluminum sol (Qilu Petrochemical catalyst is added
Factory produces, A12O3Content is 21.7 weight %), it stirs 40 minutes, obtains al binder slurries B, pH value 2.7；
Molecular sieve pulp 20Kg (the wherein 8Kg of zeolite containing ZRP, ZRP Zeolite 40, phosphorous 2.5 weight are added in slurries A
Measure the %, (RE containing rare earth2O3) 1 weight %, it is middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery product), stir to get slurries C.
Slurries C is mixed with slurries B, is stirred 30 minutes, spray drying, obtains particle B, and 500 DEG C roast 4 hours, is then washed
Free Na ion is removed, it is dry, obtain catalyst CA3.
Embodiment 4
According to the method for embodiment 1, unlike, carboxymethyl cellulose is added in al binder slurries B, and slurries A
In do not introduce carboxymethyl cellulose.Obtain catalyst CA4.
Embodiment 5
According to the method for embodiment 1, the dosage of adjustment carboxymethyl cellulose makes clay, water and carboxymethyl cellulose unlike
Carboxymethyl cellulose level is 3 weight % in the slurries that element is formed；Mashing is stirred 10 minutes after methylcellulose is added, and stands 20
Minute, it is stirred for 10 minutes, stands 15 minutes, be stirred for 10 minutes, obtain slurries A.Gained catalyst is denoted as CA5.
Embodiment 6
According to the method for embodiment 1, unlike, temperature is kept for 65-80 DEG C to slurries A in the whole process.It is catalyzed
Agent CA-6.
Comparative example 1
This comparative example prepares catalyst according to existing method, and carboxymethyl cellulose is not added.
By 30Kg decationized Y sieve water and 19Kg halloysite (Suzhou china clay company industrial products, 72.3 weight of solid content
Amount %) it is mixed with beating, 10Kg boehmite (Shandong Aluminum Plant's industrial products, 63 weight % of solid content) is added, it will with hydrochloric acid
Its PH is adjusted to 3, stirs evenly, and stands aging 1 hour at 65 DEG C, and holding PH is 2-4, cools the temperature to 55 DEG C, adds 10Kg aluminium
Colloidal sol (produce, A1 by Qilu Petrochemical catalyst plant2O3Content is 21.7 weight %), it stirs 40 minutes.Molecular sieve pulp 20Kg is added
(the wherein 8Kg of zeolite containing ZRP, ZRP Zeolite 40, phosphorous 2.5 weight the %, (RE containing rare earth2O3) 1 weight %, it is middle petrochemical industry
Catalyst asphalt in Shenli Refinery product), stirring, mashing, spray drying forming wash away free Na ion, are drying to obtain contrast medium DB-
2。
Embodiment 7-13
It will be evaluated on the FFB device of laboratory after catalyst CA1-CA6 and DB-2 aging.Catalyst aging condition: 800
DEG C, 100% steam aging 14h.Operation condition: feedstock oil be grand celebration VGO (property is shown in Table 1), 620 DEG C of reaction temperature,
Agent oil weight ratio 10, weight (hourly) space velocity (WHSV) 4h-1, 25 weight % (accounting for feedstock oil) of water injection rate.Reaction result is shown in Table 2.
1 raw material oil nature of table
2 evaluating catalyst result of table
Specific surface area, pore volume and sphericity characterization, characterization are carried out to the catalyst that embodiment 1-6 and comparative example 1 are obtained
It the results are shown in Table 3.
3 catalyst characterization result of table
。
Claims (11)
1. a kind of catalyst of producing low-carbon alkene by catalytic pyrolysis, including 10-55 weight % al binder, 15-60 weight % molecule
Sieve and 10-75 weight % clay, the molecular sieve be MFI structure zeolite or be MFI structure zeolite and y-type zeolite mixture；
The preparation method of the catalyst is the following steps are included: by al binder, clay, molecular sieve, water and carboxymethyl cellulose shape
At slurries, spray drying is optionally roasted；Wherein the weight ratio of carboxymethyl cellulose and the al binder in terms of butt is 2-40:
100；The solid content for the slurries that al binder, clay, molecular sieve, water and carboxymethyl cellulose are formed is 5-45 weight %；It is described
By al binder, clay, molecular sieve and carboxymethyl cellulose formed slurry method it is as follows: by clay, carboxymethyl cellulose
Slurries are formed with water, obtained slurries are mixed with beating with molecular sieve, are then mixed with binder, it is described by clay, carboxymethyl
Cellulose and water formation slurry processes are as follows: clay and water being mixed with beating, carboxymethyl cellulose aqueous solution is added, stirs 10-
20 minutes, stop stirring 10-20 minutes, be stirred for 10-20 minutes, stops stirring 10-20 minutes, be stirred for 10-20 minutes；It is whole
Slurry temperature is maintained at 60 DEG C or less during a.
2. catalyst described in accordance with the claim 1, which is characterized in that carboxymethyl cellulose and the al binder in terms of butt
Weight ratio is 2-40:100；The catalyst includes the weight % al binder of the 10-55 in terms of butt, the weight of the 15-55 in terms of butt %
The clay of molecular sieve and the weight of the 10-55 in terms of butt %.
3. catalyst described in accordance with the claim 1, which is characterized in that contain 15-60 weight % clay in the catalyst.
4. catalyst according to claim 1, which is characterized in that carboxymethyl cellulose weight accounts for clay, carboxymethyl cellulose
Element and water are beaten the 3-30% for the slurry weight to be formed.
5. catalyst according to claim 1, which is characterized in that the carboxymethyl cellulose weight accounts for clay, carboxymethyl
Cellulose and water are beaten the 3-10 weight % for the slurry weight to be formed.
6. catalyst according to claim 3, which is characterized in that the impurity content in the clay: Fe2O3<0.8
The weight weight of %, CaO < 0.2 weight of %, MgO < 0.5 %.
7. catalyst according to claim 3, which is characterized in that the clay is kaolin, rectorite, montmorillonite, silicon
One or more of diatomaceous earth, galapectite, saponite, sepiolite, attapulgite, hydrotalcite and bentonite.
8. catalyst described in accordance with the claim 1, which is characterized in that the molecular sieve is MFI structure zeolite or is MFI knot
The mixture of structure zeolite and y-type zeolite, on the basis of catalyst dry weight, the content of the MFI structure zeolite is 15-60 weight
% is measured, the content of the y-type zeolite is 0-45 weight %；The molar ratio of silica and aluminium oxide is 15- in the MFI structure zeolite
300:1。
9. according to the described in any item catalyst of claim 1 ~ 8, which is characterized in that by al binder, clay, molecular sieve, water
And it is 15-45 weight % that carboxymethyl cellulose, which forms the solid content of slurries,.
10. the preparation method of any one of the claim 1-9 catalyst for cracking, including by al binder, clay, molecular sieve,
Water and carboxymethyl cellulose are mixed with beating, and spray drying optionally roasts；The wherein butt of al binder, molecular sieve and clay
Weight ratio is 10-85:15-60:0-75, and the weight ratio of carboxymethyl cellulose and the al binder in terms of butt is 2-40:100；
The solid content for the slurries that al binder, clay, molecular sieve, water and carboxymethyl cellulose are formed is preferably 5-45 weight %；It is described
By al binder, clay, molecular sieve and carboxymethyl cellulose formed slurry method it is as follows: by clay, carboxymethyl cellulose
Slurries are formed with water, obtained slurries are mixed with beating with molecular sieve, are then mixed with binder, it is described by clay, carboxymethyl
Cellulose and water formation slurry processes are as follows: clay and water being mixed with beating, carboxymethyl cellulose aqueous solution is added, stirs 10-
20 minutes, stop stirring 10-20 minutes, be stirred for 10-20 minutes, stops stirring 10-20 minutes, be stirred for 10-20 minutes；It is whole
Slurry temperature is maintained at 60 DEG C or less during a.
11. a kind of method of heavy oil fluidized producing low-carbon alkene by catalytic pyrolysis, including heavy oil is contacted with catalytic cracking catalyst
The step of, which is characterized in that the catalytic cracking catalyst is catalyst provided by any one of claim 1-9.
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| CN1268591C (en) * | 2004-05-28 | 2006-08-09 | 中国石油化工股份有限公司 | Method for preparing olefin by conversion of methanol |
| CN102294261B (en) * | 2011-06-24 | 2013-07-31 | 卓润生 | Catalyst suitable for two-stage catalytic cracking reaction, and preparation method and application thereof |
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