CN105582999B - The method of catalyst of naphtha catalytic cracking production propylene and preparation method thereof and naphtha catalytic cracking production propylene - Google Patents
The method of catalyst of naphtha catalytic cracking production propylene and preparation method thereof and naphtha catalytic cracking production propylene Download PDFInfo
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Abstract
The present invention provides a kind of catalyst of naphtha catalytic cracking production propylene and preparation method thereof, and on the basis of the gross weight of the catalyst, the catalyst contains 50 95 weight % molecular sieve and 5 50 weight % matrix；The molecular sieve contains the first molecular sieve and the second molecular sieve, and first molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, and second molecular sieve is the molecular sieve with twelve-ring pore passage structure.Present invention also offers a kind of method of naphtha catalytic cracking production propylene, this method includes：Under naphtha catalytic cracking reaction condition, naphtha and water are contacted with catalyst, obtain propylene product, wherein, the catalyst includes catalyst provided by the invention.Using catalyst provided by the invention, the yield of propylene can be improved, and obtains propylene/ethylene more than 2.
Description
Technical field
The present invention relates to catalyst of naphtha catalytic cracking production propylene and preparation method thereof and naphtha catalytic cracking production
The method of propylene, in particular it relates to which a kind of catalyst of naphtha catalytic cracking production propylene, one kind prepare naphtha catalytic cracking
Produce the method for the catalyst of propylene and its obtained catalyst, and a kind of method of naphtha catalytic cracking production propylene.
Background technology
Propylene is one of most widely used basic organic chemical industry raw material, mainly for the production of polypropylene, isopropylbenzene, propylene
Nitrile, acrylic acid etc..Propylene is mainly derived from the ethylene cracker of petrochemical plant and the catalytic cracking unit of oil plant at present.With
Global propylene demand rapid growth, the yield of traditional processing technology is difficult to meet demand, therefore develops the technology of propylene enhancing
As an important development direction in petrochemical iy produced technology.
Conventional ethylene cracking is raw material by steam heat producing ethylene by cracking and propylene mainly using naphtha, wherein, by
Heat scission reaction mechanism limits, and general ethene is major product, and propylene is byproduct, and propylene/ethylene ratio is maximum limit about
0.65, higher than this ratio, total olefin will decline.This process needs to consume substantial amounts of high-quality feed naphtha, is one
The process of high energy consumption.66-70% propylene is produced with steam pyrolysis technology at present.
Catalytic pyrolysis is lower than the reaction temperature of steam thermal cracking about 50-200 DEG C, and energy consumption is relatively low.And catalytic pyrolysis
Reaction mechanism advantageously forms propylene molecules, therefore can realize naphtha production propene yield increase.
CN101491772A discloses a kind of catalyst for naphtha catalytic cracking, by weight percentage include with
Lower active component：A) 80-99.5% is selected from coexisting molecular sieve, the Intergrown molecular of ZSM-5 and β zeolites of ZSM-5 and modenite
At least one of coexisting molecular sieve of sieve or ZSM-5 and Y zeolites；Be loaded in b thereon) surplus is selected from periodic table of elements VA
At least one of race's element element or its oxide.But the diene yield of the ethene that can obtain of the catalyst and propylene is also
It is relatively low.
CN102861604A discloses a kind of producing olefin hydrocarbon by catalytic pyrolysis of naphtha catalyst, wherein, by final catalyst
Weight content meter, the EU-1/ZSM-5 composite molecular screens containing 60-90%, 0.5-3% heteropoly acid.The catalyst is actually used in
During naphtha catalytic cracking, although can be with ethene and proprene diene high income, propylene/ethylene ratio be also low, the propylene of acquisition
Yield is small.
As can be seen here, more large-tonnage propylene will be realized by carrying out naphtha catalytic cracking, it is also necessary to which new is used for naphtha
Catalytic pyrolysis produces the catalyst of propylene.
The content of the invention
During the invention aims to overcome prior art to carry out naphtha catalytic cracking production propylene, propylene yield is small
Problem, there is provided the side of catalyst of naphtha catalytic cracking production propylene and preparation method thereof and naphtha catalytic cracking production propylene
Method.
To achieve these goals, the present invention provides a kind of catalyst of naphtha catalytic cracking production propylene, with the catalysis
On the basis of the gross weight of agent, the catalyst contains 50-95 weight % molecular sieve and 5-50 weight % matrix；The molecular sieve
Containing the first molecular sieve and the second molecular sieve, first molecular sieve is the molecule with ten-ring two-dimensional elliptic type pore passage structure
Sieve, second molecular sieve is the molecular sieve with twelve-ring pore passage structure.
Present invention also offers a kind of method for the catalyst for preparing naphtha catalytic cracking production propylene, this method includes：
(1) substrate source, water and optional acid solution are mixed, forms slurries；
(2) molecular sieve or suspension containing molecular sieve and water are mixed with the slurries, obtained catalyst mixing
Thing is molded, and optional is dried and is calcined；
The molecular sieve contains the first molecular sieve and the second molecular sieve, and first molecular sieve is ellipse with ten-ring two dimension
The molecular sieve of round pore passage structure, second molecular sieve are the molecular sieve with twelve-ring pore passage structure.
Present invention also offers a kind of method for the catalyst for preparing naphtha catalytic cracking production propylene, this method includes：
(1) substrate source, water, the first molecular sieve and optional acid solution are mixed, forms slurries；
(2) the second molecular sieve or suspension containing the second molecular sieve and water are mixed with the slurries, what is obtained urges
Agent mixture is molded, and optional is dried and is calcined；
First molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, and second molecular sieve is
Molecular sieve with twelve-ring pore passage structure.
Present invention also offers catalyst made from method provided by the present invention.
Present invention also offers a kind of method of naphtha catalytic cracking production propylene, this method includes：It is catalyzed in naphtha
Under crack reacting condition, naphtha and water are contacted with catalyst, obtain propylene product, wherein, the catalyst includes this hair
The catalyst of bright offer.
Using catalyst provided by the invention, the yield of propylene can be improved, and obtains propylene/ethylene more than 2.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of catalyst of naphtha catalytic cracking production propylene, using the gross weight of the catalyst as base
Standard, the catalyst contain 50-95 weight % molecular sieve and 5-50 weight % matrix；The molecular sieve contains the first molecular sieve
With the second molecular sieve, first molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, described second point
Son sieve is the molecular sieve with twelve-ring pore passage structure.
In catalyst provided by the invention, using foregoing first molecular sieve and the second molecular sieve as catalytic cracking activity group
Point, the yield that higher naphtha catalytic cracking produces propylene can be obtained.
According to the present invention, first molecular sieve has ten-ring two-dimensional elliptic type hole road, and preferably channel openings diameter exists
0.45-0.56 nanometers.
, according to the invention it is preferred to first molecular sieve is the molecular sieve of FER structures and/or the molecular sieve of MFS structures.Knot
Structure type FER and MFS refer to the molecular sieve structure of International Zeolite Association meeting (IZA) name, for describing duct in molecular sieve
Space expanding.The molecular sieve of the FER structures includes ZSM-35 zeolites, Ferrierite zeolites, FU-9 zeolites, ISI-6
Zeolite, NU-23 zeolites and Sr-D zeolites etc., the molecular sieve of MFS structures include ZSM-57 zeolites and COK-5 zeolites etc..
It is preferred that first molecular sieve is ZSM-35 zeolites, Ferrierite zeolites, FU-9 zeolites, ISI-6 zeolites, NU-
At least one of 23 zeolites, Sr-D zeolites, ZSM-57 zeolites and COK-5 zeolites.
, according to the invention it is preferred to first molecular sieve for FER structures molecular sieve and MFS structures molecular sieve mixing
Thing.It is further preferred that the weight ratio of the molecular sieve of the FER structures and the molecular sieve of MFS structures is 0.1-10:1, more preferably 1-5:
1。
The molecular sieve of more preferably described FER structures is ZSM-35 zeolites, Ferrierite zeolites, FU-9 zeolites, ISI-6 boilings
At least one of stone, NU-23 zeolites and Sr-D zeolites, more preferably ZSM-35 zeolites, Ferrierite zeolites and FU-
At least one of 9 zeolites.
More preferably the molecular sieve of MFS structures is at least one of ZSM-57 zeolites and COK-5 zeolites.
According to a kind of preferred embodiment of the present invention, the molecular sieves of preferably described FER structures for ZSM-35 zeolites and
The mixture of Ferrierite zeolites, more preferably the weight ratio of the two are 2-5:1；The molecular sieve of the MFS structures is ZSM-57
The mixture of zeolite and COK-5 zeolites, more preferably the weight ratio of the two are 2-5:1.
In the present invention, the sial atomic molar ratio (Si/Al) of first molecular sieve can be 0.1-100：1；Preferably
30-80:1。
In accordance with the present invention it is preferred that a diameter of 0.65-0.7 nanometers of the channel openings of second molecular sieve.More preferably
Ground, second molecular sieve be selected from AET, AFR, AFS, AFI, BEA, BOG, CFI, CON, GME, IFR, ISV, LTL, MEI,
At least one of zeolite or non-zeolite molecular sieve of MOR, OFF, SAO structure.It is particularly preferred that second molecular sieve is
At least one of Beta, SAPO-5, SAPO-40, SSZ-13, CIT-1, ITQ-7, ZSM-18, modenite and sodium chabazite.
In the present invention, sial atomic molar ratio (Si/Al) can be 0.1-100 in second molecular sieve：1；Preferably
30-80:1。
In the case of, according to the invention it is preferred to, the weight ratio of first molecular sieve and second molecular sieve is 0.1-15：
1, preferably 1-5：1.
In accordance with the present invention it is preferred that on the basis of the gross weight of the catalyst, the catalyst contains 60-90 weights
Measure % molecular sieve and 10-40 weight % matrix.
In the case of, according to the invention it is preferred to, the matrix can be selected from aluminum oxide, silica, amorphous silica-alumina, oxidation
At least one of zirconium, titanium oxide, boron oxide and alkaline earth oxide.
Meet that the purpose of the present invention can be achieved in the catalyst of aforementioned claim of the present invention, the present invention is to its preparation method without spy
Different to require, according to a kind of preferred embodiment of the present invention, the catalyst is prepared as follows：(1) by substrate source, water
Mixed with optional acid solution, form slurries；
(2) molecular sieve or suspension containing molecular sieve and water are mixed with the slurries, obtained catalyst mixing
Thing is molded, and optional is dried and is calcined；
The molecular sieve contains the first molecular sieve and the second molecular sieve, and first molecular sieve is ellipse with ten-ring two dimension
The molecular sieve of round pore passage structure, second molecular sieve are the molecular sieve with twelve-ring pore passage structure.
According to a kind of preferred embodiment of the present invention, preferably catalyst of the invention is prepared as follows：
(1) substrate source, water, the first molecular sieve and optional acid solution are mixed, forms slurries；
(2) the second molecular sieve or suspension containing the second molecular sieve and water are mixed with the slurries, what is obtained urges
Agent mixture is molded, and optional is dried and is calcined；
First molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, and second molecular sieve is
Molecular sieve with twelve-ring pore passage structure.
The method according to the invention, the species and its dosage of first molecular sieve and the second molecular sieve are urged described above
It has been discussed in detail during agent, not repeated description herein.
In the case of, according to the invention it is preferred to, the substrate source can be can under conditions of the roasting of step (2)
It is changed into the material of matrix, the matrix is aluminum oxide, silica, amorphous silica-alumina, zirconium oxide, titanium oxide, boron oxide and alkali
At least one of soil metal oxide；The substrate source and the addition of the molecular sieve cause in obtained catalyst, with
On the basis of the gross weight of the catalyst, the content of matrix is 5-50 weight %, and the content of molecular sieve is 50-95 weight %.
In one embodiment of the present invention, silica source and alumina source can be used to prepare catalyst provided by the invention
In matrix.
In one embodiment of the invention, the silica source can be that silica or silica content are more than 45 weights
Measure % natural crystal.Preferably, the silica source can be laminated clay column, diatomite, expanded perlite, silicalite, silicon
At least one of colloidal sol, macropore silicon oxide and silica gel.
In one embodiment of the invention, the alumina source can be the condition in the roasting of step (2)
The material of aluminum oxide can be changed into down.Preferably, the alumina source is in boehmite, hydrated alumina and Alumina gel
One or more；The hydrated alumina is boehmite, false boehmite, hibbsite and amorphous hydrogen-oxygen
Change at least one of aluminium.
In one embodiment of the invention, the summation of the amount of silica and aluminum oxide in the catalyst obtained is designated as
The amount of matrix.In addition, although containing aluminum oxide and silica in the molecular sieve, but the silica contained in the molecular sieve
It still can be regarded as the amount of the molecular sieve with the amount of aluminum oxide, be not counted in silica and aluminum oxide.Method i.e. provided by the present invention
The content of each component is calculated according to inventory in obtained catalyst.
In the present invention, optional acid solution described in step (1) can select to be acidified using acid solution according to substrate source
Or it is acidified without using acid solution.In one embodiment, when using Alumina gel and/or Ludox as substrate source (aluminum oxide
Source or/or silica source) when, it can be acidified without using acid solution；When using boehmite and/or kaolin, it can make
It is acidified with acid solution.The dosage of the acid solution can make it that the pH value of the slurries is 1-5, preferably 1.5-4.The acid is molten
Liquid can be selected from water-soluble inorganic acid and/or organic acid, for example, can be in hydrochloric acid, nitric acid, phosphoric acid and acetic acid at least
It is a kind of.
In the present invention, the amount of water is added in step (1) to be not specially limited, as long as institute in step (1) can be obtained
The slurries stated.Such as add the amount of water to make the solid contents of the obtained slurries be 10-60 weight %, preferably 10-35
Weight %.
In the present invention, the addition that the water of the suspension is formed in step (2) can be so that there is no particular limitation, as long as energy
Access the suspension described in step (2).Such as add the amount of water to make the solid content of the obtained suspension be 10-
60 weight %.
In step (2) of the present invention, the catalyst mixture can be wet mixture, paste mixture, dough or slurry
The forms such as liquid.By the shaping, the catalyst mixture can be shaped to extrudate, piece, pill, ball or microspheroidal
Grain.For example, when the catalyst mixture is dough or paste mixture, the catalyst mixture shaping can be made (preferably
Extrusion molding) particle is formed, for preferably diameter in 1.0-8.0mm, then length makes institute in 2.0-5.0mm cylindrical extrudates
The extrudate obtained is dried, is calcined.It if the catalyst mixture is wet mixture form, can be thickened the mixture,
By drying aftershaping.Can be using the catalyst mixture as slurry form, it is 20-200 to form granularity by spray drying
The microballoon of micron, reach the purpose of shaping.For the ease of spray drying, drying the solid content of procatalyst mixture can be
10-50 weight %, preferably 20-50 weight %.
In the present invention, the drying means and condition of the catalyst mixture are known to those skilled in the art, for example,
Dry method can be dry, dry, forced air drying.Under preferable case, in step (2), dry temperature can be room temperature
To 400 DEG C, preferably 100-350 DEG C；The time of the drying is at least 0.5 hour, preferably 0.5-60 hours.
In the present invention, the roasting condition of the catalyst mixture can also be known to those skilled in the art, typically
For, the temperature of the roasting is 400-700 DEG C, preferably 450-650 DEG C；The time of the roasting is at least 0.5 hour, excellent
Elect 0.5-100 hours, more preferably 0.5-10 hours as.
Present invention also offers catalyst made from method provided by the present invention.
According to the present invention, on the basis of the gross weight of the catalyst, the catalyst contain matrix (such as silica and/or
Aluminum oxide) total content be 5-50 weight %, the content of molecular sieve is 50-95 weight %；The molecular sieve contains the first molecule
Sieve and the second molecular sieve, first molecular sieve are the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, described second
Molecular sieve is zeolite and/or non-zeolite molecular sieve with twelve-ring duct；Preferably, matrix (such as silica and/or oxygen
Change aluminium) total content be 10-40 weight %, the content of molecular sieve is 60-90 weight %.
Present invention also offers a kind of method of naphtha catalytic cracking production propylene, this method includes：It is catalyzed in naphtha
Under crack reacting condition, naphtha and water are contacted with catalyst, obtain propylene product, wherein, the catalyst includes this hair
The catalyst of bright offer.
In the case of, according to the invention it is preferred to, the naphtha catalytic cracking reaction condition includes：Temperature is 520-590 DEG C,
Pressure is 0.1-0.2MPa, and water/oily feed weight ratio is 0.3-2, and naphtha feed weight (hourly) space velocity (WHSV) is 2-40h-1。
In the case of, according to the invention it is preferred to, the naphtha contains 0.5-1.5 weight % alkene, 40-60 weight %
Alkane, 20-40 weight % cycloalkane and 10-20 weight % aromatic hydrocarbons.
The present invention will be described in detail by way of examples below.
Gas-phase product property is by gas chromatography in following examples, using the instrument of Agilent company HP6890 models
Device determines.Yield and the logical below equation of selectivity are calculated：
Yield=(purpose product such as (C2 =+C3 =) growing amount/reaction-ure feeding amount) × 100%
Selectivity=(purpose product such as (C2 =~C4 =) growing amount/reactant inversion quantity) × 100%
Embodiment 1
The present embodiment is used for the preparation method for illustrating catalyst provided by the invention and naphtha catalytic cracking produces propylene
Method.
(1) catalyst is prepared.28 grams of boehmite (Shandong Aluminum Plant, containing butt 20 grams) and 50 grams of deionized waters are existed
Stirring is lower to be mixed, and it is small to add concentrated hydrochloric acid (chemistry is pure, and Beijing Chemical Plant produces) stirring acidifying 1 that 3.6 grams of concentration are 36 weight %
When after be warming up to 60 DEG C be acidified 1 hour, pH value 3.0.When temperature is reduced to below 40 DEG C, addition contains 50 grams of ZSM- respectively
35 zeolites (Shanghai Zhuo Yue Chemical Co., Ltd.s, Si/Al mol ratio=30：1) (made by oneself, Si/Al mol ratios with 30 grams of Beta zeolites
=50：1) suspension (solid content of ZSM-35 zeolites and Beta zeolites is respectively 35 weight % and 21 weight %), after mixing
Stirring obtains catalyst mixture in 1 hour.
The catalyst mixture uses single-screw extruder extruded moulding pelletizing, dries at room temperature, and 5 are dried at 120 DEG C
After hour, it is calcined 1 hour at 480 DEG C and obtains catalyst.
Catalyst composition calculates by feeding intake：ZSM-35 zeolites and Beta zeolite total contents are respectively 50 weight %, 30 weights
% is measured, matrix (aluminum oxide) content is 20 weight %.
(2) propylene is produced.By Catalyst packing made from step (1) into fixed bed reactors, by naphtha (olefin-containing 1
Weight %, containing the weight % of alkane 56, containing the weight % of cycloalkane 32, containing the weight % of aromatic hydrocarbons 11, the μ g/g of basic nitrogen 0.5) and water through 250
DEG C preheating after inject fixed bed reactors in；Catalyst made from step (1) is added in fluidized-bed reactor with fluidizing state, its
In, the weight (hourly) space velocity (WHSV) of naphtha injection is 2.3hr-1, water/oily feed weight ratio is 0.46.Reaction temperature is 520 DEG C, and pressure is
0.2MPa.Reaction result is shown in Table 1.
Embodiment 2
The present embodiment is used for the preparation method for illustrating catalyst provided by the invention and naphtha catalytic cracking produces propylene
Method.
(1) catalyst is prepared.Contain Ferrierite zeolites (Si/Al mol ratio=50 by 32 grams：1) boiled with 32 grams of mercerisings
Stone molecular sieve (Shanghai Shen Tan environmental friendly materials Co., Ltd, Si/Al mol ratio=80：1) mechanical mixture uniformly adds afterwards contains 7 grams
The Ludox (solid content is 30 weight %) of silica, through compression molding, obtains catalyst.
Catalyst composition calculates by feeding intake：Ferrierite and modenite content are respectively 45 weight %, 45 weight %, oxygen
SiClx matrix content is 10 weight %.
(2) propylene is produced.By Catalyst packing made from step (1) into fixed bed reactors, by naphtha (olefin-containing 1
Weight %, containing the weight % of alkane 56, containing the weight % of cycloalkane 32, containing the weight % of aromatic hydrocarbons 11, the μ g/g of basic nitrogen 0.5) and water through 250
DEG C preheating after inject fixed bed reactors in.Catalyst made from step (1) is added in fluidized-bed reactor with fluidizing state, its
In, the weight (hourly) space velocity (WHSV) of naphtha injection is 36.5hr-1, water/oily feed weight ratio is 0.96.Reaction temperature is 570 DEG C, and pressure is
0.1MPa.Reaction result is shown in Table 1.
Embodiment 3
The present embodiment is used for the preparation method for illustrating catalyst provided by the invention and naphtha catalytic cracking produces propylene
Method.
(1) catalyst is prepared.
By boehmite 21 grams of (catalyst Nanjing branch company, salic 15 grams of butt), 32 grams of kaolin (catalyst
Asphalt in Shenli Refinery, 25 grams of silicon oxide-containing butt) and 90 grams of deionized waters mix under agitation, add 4.0 grams of concentrated nitric acids (chemistry
It is pure, Beijing Chemical Plant produce) stirring acidifying 1 hour after be warming up to 60 DEG C be acidified 1 hour, pH value 2.8.Treat that temperature is reduced to 40
When below DEG C, add containing 50 grams of ZSM-57 zeolites (self-control, Si/Al mol ratio=80：And 10 grams of ZSM-18 zeolites (Shandong 1)
Zibo molecular sieve factory, Si/Al mol ratio=40：1) suspension, ZSM-57 zeolites and the respective solid content of ZSM-18 zeolites are
25 weight % and 5 weight %, stirred 1 hour after mixing and obtain catalyst mixture.
The catalyst mixture uses Niro Bowen Nozzle TowerTMThe spray dryer of model is sprayed
Dry, spray drying pressure is 8.5 to 9.5MPa, and below 500 DEG C of inlet temperature, outlet temperature is about 150 DEG C.By being spray-dried
Obtained microballoon is first dried 1 hour at 150 DEG C, is then calcined 1 hour at 480 DEG C and is obtained catalyst.
Catalyst composition calculates by feeding intake：ZSM-57 and ZSM-18 molecular sieve contents are respectively 50 weight %, 10 weight %,
Matrix (aluminum oxide+kaolin) content is 40 weight %.
(2) propylene is produced.By naphtha (the weight % of olefin-containing 1, containing the weight % of alkane 56, containing the weight % of cycloalkane 32, containing virtue
The weight % of hydrocarbon 11, the μ g/g of basic nitrogen 0.5) and water through 250 DEG C preheating after inject fluidized-bed reactor in.By (1) obtained catalysis
Agent is added in fluidized-bed reactor with fluidizing state, and the weight (hourly) space velocity (WHSV) of wherein naphtha injection is 4.6hr-1, water/oily feed weight ratio
For 1.61.Reaction temperature is 590 DEG C, pressure 0.1MPa.Reaction result is shown in Table 1.
Embodiment 4
According to the method cracking naphtha of embodiment 3, the difference is that, the first molecular sieve is by ZSM-35 zeolites in catalyst
(sial atomic molar ratio is 30) and COK-5 zeolites (sial atomic molar ratio is 50) replace, and the part by weight of the two is 1:
1。
Embodiment 5
According to the method cracking naphtha of embodiment 3, the difference is that, the first molecular sieve is boiled by Ferrierite in catalyst
Stone (sial atomic molar ratio is 50) and ZSM-57 zeolites (sial atomic molar ratio is 80) replace, and the part by weight of the two is
2:1。
Embodiment 6
According to the method cracking naphtha of embodiment 3, the difference is that, the first molecular sieve is by FU-9 zeolite (silicon in catalyst
50) aluminium atom mol ratio is replaces with ZSM-57 zeolites (sial atomic molar ratio is 30), and the part by weight of the two is 5:1.
Embodiment 7
According to the method cracking naphtha of embodiment 4, unlike, in catalyst in the first molecular sieve ZSM-35 zeolites by
The mixture generation of ZSM-35 zeolites (sial atomic molar ratio is 30) and Ferrierite zeolites (sial atomic molar ratio is 30)
Replace, the weight ratio of the two is 3:1；COK-5 zeolites are by ZSM-57 zeolites (sial atomic molar ratio is 50) and COK-5 zeolite (silicon
Aluminium atom mol ratio replaces for mixture 50), and the weight ratio of the two is 4:1.
Embodiment 8
The present embodiment is used for the preparation method for illustrating catalyst provided by the invention and naphtha catalytic cracking produces propylene
Method.
(1) catalyst is prepared, catalyst is prepared according to the method for embodiment 6, unlike, the first molecular sieve and second point
Son screening, which is opened, to feed intake, specific as follows：
By boehmite 21 grams of (catalyst Nanjing branch company, salic 15 grams of butt), 32 grams of kaolin (catalyst
Asphalt in Shenli Refinery, 25 grams of silicon oxide-containing butt), 50 gram of first molecular sieve FU-9 zeolite (sial atomic molar ratio is 50) and ZSM-
57 zeolites (sial atomic molar ratio is 30), and the part by weight of the two is 5:1 and 257 gram of deionized water mixes under agitation,
Add 11.4 grams of concentrated nitric acids (chemistry is pure, and Beijing Chemical Plant produces) stirring acidifying to be warming up to 60 DEG C after 1 hour and be acidified 1 hour, pH
It is worth for 2.8.When temperature is reduced to below 40 DEG C, addition contains 10 grams of ZSM-18 zeolites (Shandong Zibo molecular sieve factory, Si/Al
Mol ratio=40：1) suspension, the solid content of ZSM-18 zeolites is 30 weight %, is stirred 1 hour after mixing and obtains catalyst
Mixture.
The catalyst mixture uses Niro Bowen Nozzle TowerTMThe spray dryer of model is sprayed
Dry, spray drying pressure is 8.5 to 9.5MPa, and below 500 DEG C of inlet temperature, outlet temperature is about 150 DEG C.By being spray-dried
Obtained microballoon is first dried 1 hour at 150 DEG C, is then calcined 1 hour at 480 DEG C and is obtained catalyst.
Catalyst composition calculates by feeding intake：First molecular sieve and ZSM-18 molecular sieve contents are respectively 50 weight %, 10 weights
% is measured, matrix (aluminum oxide+kaolin) content is 40 weight %.
(2) propylene is produced.By naphtha (the weight % of olefin-containing 1, containing the weight % of alkane 56, containing the weight % of cycloalkane 32, containing virtue
The weight % of hydrocarbon 11) and water through 250 DEG C preheating after inject fluidized-bed reactor in.Catalyst made from (1) is added with fluidizing state
In fluidized-bed reactor, wherein, the weight (hourly) space velocity (WHSV) of naphtha injection is 4.6hr-1, water/oily feed weight ratio is 1.61.Reaction temperature
Spend for 590 DEG C, pressure 0.1MPa.Reaction result is shown in Table 1.
Comparative example 1
According to the method for embodiment 1, the difference is that, ZSM-35 zeolites are replaced by the Beta zeolites of equivalent, i.e., molecular sieve is complete
Portion is the second molecular sieve.
Comparative example 2
According to the method for embodiment 1, the difference is that, Beta zeolites are replaced by the ZSM-35 zeolites of equivalent, i.e., molecular sieve is complete
Portion is the first molecular sieve.
Table 1
Catalyst provided by the invention, which is can be seen that, from the data result of table 1 contains the first molecular sieve and the second molecular sieve,
In naphtha catalytic cracking production propylene is carried out, high ethene and propene yield can be obtained, and wherein propylene/ethylene is than big
In 2, it is possible to achieve producing more propylene.
Claims (23)
1. a kind of catalyst of naphtha catalytic cracking production propylene, on the basis of the gross weight of the catalyst, the catalyst contains
50-95 weight % molecular sieve and 5-50 weight % matrix；The molecular sieve contains the first molecular sieve and the second molecular sieve, institute
It is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure to state the first molecular sieve, and second molecular sieve is with ten binary
The molecular sieve of ring pore passage structure；First molecular sieve is the mixture of the molecular sieve and the molecular sieve of MFS structures of FER structures；
The weight ratio of first molecular sieve and second molecular sieve is 0.1-15：1.
2. catalyst according to claim 1, wherein, the weight ratio of the molecular sieve of FER structures and the molecular sieve of MFS structures
For 0.1-10:1.
3. catalyst according to claim 1, wherein, the weight ratio of the molecular sieve of FER structures and the molecular sieve of MFS structures
For 1-5:1.
4. according to the catalyst described in any one in claim 1-3, wherein, the molecular sieve of the FER structures is ZSM-35
At least one of zeolite, Ferrierite zeolites, FU-9 zeolites, ISI-6 zeolites, NU-23 zeolites and Sr-D zeolites；MFS is tied
The molecular sieve of structure is at least one of ZSM-57 zeolites and COK-5 zeolites.
5. according to the catalyst described in any one in claim 1-3, wherein, the molecular sieve of the FER structures is ZSM-35
One kind in zeolite, Ferrierite zeolites and FU-9 zeolites.
6. according to the catalyst described in any one in claim 1-3, wherein, the molecular sieve of the FER structures is ZSM-35
The mixture of zeolite and Ferrierite zeolites；The molecular sieve of the MFS structures is the mixing of ZSM-57 zeolites and COK-5 zeolites
Thing.
7. according to the catalyst described in any one in claim 1-3, wherein, the channel openings diameter of second molecular sieve
For 0.6-0.75 nanometers.
8. catalyst according to claim 7, wherein, second molecular sieve be selected from AET, AFR, AFS, AFI,
In the zeolite or non-zeolite molecular sieve of BEA, BOG, CFI, CON, GME, IFR, ISV, LTL, MEI, MOR, OFF, SAO structure extremely
Few one kind.
9. according to the catalyst described in any one in claim 1-3, wherein, should on the basis of the gross weight of the catalyst
Catalyst contains 60-90 weight % molecular sieve and 10-40 weight % matrix.
10. according to the catalyst described in any one in claim 1-3, wherein, the matrix be selected from aluminum oxide, silica,
At least one of amorphous silica-alumina, zirconium oxide, titanium oxide, boron oxide and alkaline earth oxide.
11. a kind of method for the catalyst for preparing naphtha catalytic cracking production propylene, this method include：
(1) substrate source, water and optional acid solution are mixed, forms slurries；
(2) molecular sieve or suspension containing molecular sieve and water are mixed with the slurries, obtained catalyst mixture enters
Row shaping, optional is dried and is calcined；
The molecular sieve contains the first molecular sieve and the second molecular sieve, and first molecular sieve is with ten-ring two-dimensional elliptic type
The molecular sieve of pore passage structure, second molecular sieve are the molecular sieve with twelve-ring pore passage structure；First molecular sieve
For the mixture of the molecular sieve and the molecular sieve of MFS structures of FER structures；The weight of first molecular sieve and second molecular sieve
It is 0.1-15 to measure ratio：1.
12. a kind of method for the catalyst for preparing naphtha catalytic cracking production propylene, this method include：
(1) substrate source, water, the first molecular sieve and optional acid solution are mixed, forms slurries；
(2) the second molecular sieve or suspension containing the second molecular sieve and water are mixed with the slurries, obtained catalyst
Mixture is molded, and optional is dried and is calcined；
First molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, second molecular sieve be with
The molecular sieve of twelve-ring pore passage structure；First molecular sieve is the molecular sieve of FER structures and mixing for the molecular sieve of MFS structures
Compound；The weight ratio of first molecular sieve and second molecular sieve is 0.1-15：1.
13. the method according to claim 11 or 12, wherein, the weight of the molecular sieve of FER structures and the molecular sieve of MFS structures
It is 0.1-10 to measure ratio:1.
14. the method according to claim 11, wherein, the weight ratio of the molecular sieve of FER structures and the molecular sieve of MFS structures
For 1-5:1.
15. the method according to claim 11 or 12, wherein, the molecular sieves of the FER structures is ZSM-35 zeolites,
At least one of Ferrierite zeolites, FU-9 zeolites, ISI-6 zeolites, NU-23 zeolites and Sr-D zeolites；Point of MFS structures
Son sieve is at least one of ZSM-57 zeolites and COK-5 zeolites.
16. the method according to claim 11 or 12, wherein, the molecular sieves of the FER structures is ZSM-35 zeolites,
One kind in Ferrierite zeolites and FU-9 zeolites.
17. the method according to claim 11 or 12, wherein, the molecular sieves of the FER structures for ZSM-35 zeolites and
The mixture of Ferrierite zeolites；The molecular sieve of the MFS structures is the mixture of ZSM-57 zeolites and COK-5 zeolites.
18. the method according to claim 11 or 12, wherein, a diameter of 0.6- of channel openings of second molecular sieve
0.75 nanometer.
19. according to the method for claim 18, wherein, second molecular sieve be selected from AET, AFR, AFS, AFI,
In the zeolite or non-zeolite molecular sieve of BEA, BOG, CFI, CON, GME, IFR, ISV, LTL, MEI, MOR, OFF and SAO structure
It is at least one.
20. the method according to claim 11 or 12, wherein, the substrate source is the bar in the roasting of step (2)
The material of matrix can be changed under part, the matrix is aluminum oxide, silica, amorphous silica-alumina, zirconium oxide, titanium oxide, oxygen
Change at least one of boron and alkaline earth oxide；The substrate source and the addition of the molecular sieve cause obtained catalysis
In agent, on the basis of the gross weight of the catalyst, the content of matrix is 5-50 weight %, and the content of molecular sieve is 50-95 weights
Measure %.
21. the catalyst as made from the method described in any one in claim 11-20.
22. a kind of method of naphtha catalytic cracking production propylene, this method include：Under naphtha catalytic cracking reaction condition,
Naphtha and water are contacted with catalyst, obtain propylene product, it is characterised in that the catalyst include claim 1-10 and
Catalyst in 21 described in any one.
23. according to the method for claim 22, wherein, the naphtha catalytic cracking reaction condition includes：Temperature is
520-590 DEG C, pressure 0.1-0.2MPa, water/oily feed weight ratio is 0.3-2, and naphtha feed weight (hourly) space velocity (WHSV) is 2-40h-1。
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| CN101491772A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Catalyst for naphtha catalytic cracking |
| CN101514022A (en) * | 2008-02-20 | 2009-08-26 | 中国石油化工股份有限公司 | ZSM-5/ZSM-23/MCM-22 triphase coexisting molecular sieve and method for synthesizing same |
| CN102451731A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation and application of coating slurry for cellular carrier catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101491772A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Catalyst for naphtha catalytic cracking |
| CN101514022A (en) * | 2008-02-20 | 2009-08-26 | 中国石油化工股份有限公司 | ZSM-5/ZSM-23/MCM-22 triphase coexisting molecular sieve and method for synthesizing same |
| CN102451731A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation and application of coating slurry for cellular carrier catalyst |
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