CN105582997B - 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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- CN105582997B CN105582997B CN201410563150.3A CN201410563150A CN105582997B CN 105582997 B CN105582997 B CN 105582997B CN 201410563150 A CN201410563150 A CN 201410563150A CN 105582997 B CN105582997 B CN 105582997B
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Abstract
The present invention provides a kind of catalyst of naphtha catalytic cracking production propylene and preparation method thereof, which includes ordered structure carrier and the active component coating for being distributed in ordered structure inner surface of the carrier and/or outer surface；The molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure.The present invention also provides a kind of methods of naphtha catalytic cracking production propylene.Using catalyst provided by the invention, the yield of propylene can be improved, and obtains propylene/ethylene more than 1.
Description
Technical field
Catalyst the present invention relates to naphtha catalytic cracking production propylene and preparation method thereof and naphtha catalytic cracking production
The method of propylene, and in particular, to a kind of catalyst of naphtha catalytic cracking production propylene, it is a kind of to prepare naphtha catalytic cracking
Produce the method for the catalyst of propylene and its method of catalyst obtained and a kind 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 be raw material by steam heat producing ethylene by cracking and propylene mainly using naphtha, wherein being heated
Cracking reaction mechanism limits, and general ethylene 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 a high energy consumption
Process.The propylene of 66-70% is produced with steam pyrolysis technology at present.
Catalytic pyrolysis is about 50-200 DEG C lower than the reaction temperature of steam thermal cracking, and energy consumption is relatively low.And catalytic pyrolysis
Reaction mechanism advantageously forms propylene molecules, therefore can realize that naphtha production propene yield increases.
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 selected from periodic table of elements VA
At least one of race's element element or its oxide.But the diene yield of the ethylene 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%, the heteropoly acid of 0.5-3%.The catalyst is actually used in
During naphtha catalytic cracking, although can be with ethylene and proprene diene high income, propylene/ethylene ratio be also low, the propylene of acquisition
Yield is small.
It can be seen that 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 purpose of the invention is to which the prior art being overcome to carry out naphtha catalytic cracking production propylene, propylene yield is small
Problem provides 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, the catalyst
Including ordered structure carrier and the active component coating for being distributed in ordered structure inner surface of the carrier and/or outer surface；It is urged with described
On the basis of the total weight of agent, the content of the active component coating is 10-50 weight %；With the total of the active component coating
On the basis of weight, the active component coating contains the molecular sieve of 50-95 weight % and the matrix of 5-50 weight %；The molecule
It sieves as the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure.
The present invention also provides a kind of method for the catalyst for preparing naphtha catalytic cracking production propylene, this method includes：
(1) molecular sieve and aqueous solvent are mixed and ground, obtain molecular sieve pulp, the molecular sieve is with ten-ring two-dimensional elliptic
The molecular sieve of type pore passage structure；(2) molecular sieve pulp with the substrate source is mixed, forms active component coating slurries；
(3) with active component coating slurries coating ordered structure carrier and drying and roasting.
The present invention also provides catalyst made from method provided by the present invention.
The present invention also provides 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 with catalyst are contacted, obtain propylene product, wherein, the catalyst is the present invention
The catalyst of offer.
Using catalyst provided by the invention, the yield of propylene can be improved, and obtains propylene/ethylene more than 1.Example
In embodiment 1, the activity using ordered structure carrier and containing the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure
The catalyst of component coating, in the product that naphtha catalytic cracking obtains, C2 =-C4 =Selectivity be 90.8%, C2 =+C3 ='s
Yield is 68.23%, C3 =/C2 =For 1.7, producing more propylene can be realized.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific 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.
In the present invention, refer to include ordered structure carrier using term ordered structure catalyst and be distributed in inner surface of the carrier
And/or the catalyst of the active component coating of outer surface；Ordered structure carrier is such as honeycomb substrate of the carrier with ordered structure；
Monolithic reactors are the fixed bed reactors for having loaded ordered structure catalyst as catalyst bed.
The present invention provides a kind of catalyst of naphtha catalytic cracking production propylene, which includes ordered structure carrier
With the active component coating for being distributed in ordered structure inner surface of the carrier and/or outer surface；Using the total weight of the catalyst as base
Standard, the content of the active component coating is 10-50 weight %；It is described on the basis of the total weight of the active component coating
Active component coating contains the molecular sieve of 50-95 weight % and the matrix of 5-50 weight %；The molecular sieve is with ten-ring
The molecular sieve of two-dimensional elliptic type pore passage structure.
The present invention has the molecular sieve of ten-ring two-dimensional elliptic type pore passage structure, is preferably a kind of work of FER or MFS structures
For catalytic cracking activity component, and active component coating is made in molecular sieve and matrix and is distributed on ordered structure carrier, shape
Into ordered structure catalyst, the yield that higher naphtha catalytic cracking produces propylene can be obtained.
According to the present invention, the molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, preferably duct
Opening diameter is at 0.45-0.56 nanometers.
, according to the invention it is preferred to the molecular sieve is the molecular sieve of FER structures and/or the molecular sieve of MFS structures.Structure class
Type FER and MFS refer to the molecular sieve structure of International Zeolite Association meeting (IZA) name, for describing the space in duct in molecular sieve
Topological structure.The molecular sieve of the FER structures include ZSM-35 zeolites, Ferrierite zeolites, FU-9 zeolites, ISI-6 zeolites,
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 the molecular sieve is ZSM-35 zeolites, Ferrierite zeolites, FU-9 zeolites, ISI-6 zeolites, NU-23 boiling
At least one of stone, Sr-D zeolites, ZSM-57 zeolites and COK-5 zeolites.
, according to the invention it is preferred to mixture of the molecular sieve for the molecular sieve of the molecular sieve and MFS structures of FER structures.
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 the more preferable FER structures is ZSM-35 zeolites, Ferrierite zeolites, FU-9 zeolites, ISI-6 boiling
At least one of stone, NU-23 zeolites and Sr-D zeolites, further preferably ZSM-35 zeolites, Ferrierite zeolites and FU-
At least one of 9 zeolites.
The molecular sieve of more preferable MFS structures is at least one of ZSM-57 zeolites and COK-5 zeolites.
According to a preferred embodiment of the present invention, the molecular sieve of preferably described FER structures for ZSM-35 zeolites and
The mixture of Ferrierite zeolites, the more preferably 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, the more preferably weight ratio of the two are 2-5:1.
In the present invention, the sial atomic molar ratio (Si/Al) of the molecular sieve can be 0.1-100：1；Preferably 30-
80:1。
In accordance with the present invention it is preferred that on the basis of the total weight of the active component coating, the active component coating contains
There are the molecular sieve of 54-90 weight % and the matrix of 10-46 weight %.
In accordance with the present invention it is preferred that on the basis of the total weight of the catalyst, the content of the active component coating is
15-30 weight %.
According to the present invention, the ordered structure carrier can be used for providing catalyst bed in fixed bed reactors.The rule
Whole structure carrier can be the carrier block of monoblock, and inside forms hollow pore passage structure, can be distributed catalysis on the inner wall in duct
Agent coating, duct space may be used as the flowing space of fluid.Under preferable case, the ordered structure carrier, which is selected from, has both ends
The monolithic substrate of the parallel channels structure of opening.The ordered structure carrier can be the honeycomb that section has cellular perforate
The regular carrier of formula (abbreviation honeycomb substrate).
In the case of, according to the invention it is preferred to, the hole density in the section of the ordered structure carrier for 6-140 holes/square li
Rice is preferably 20-100 holes/square centimeter；The sectional area in each hole is 0.4-10 square millimeters, is preferably 2-7 square millimeters；
Percent opening is 50-80%.The shape in hole can be square (or wing square, i.e., the center of four edges in square hole
There is an inside wing of vertical edges in position, the 1/5-2/5 of the length of square length of side), equilateral triangle, regular hexagon, circle and ripple
One kind in line shape.
In the case of, according to the invention it is preferred to, the ordered structure carrier can be selected from cordierite honeycomb carrier, mullite bee
At least one of nest carrier, cellular alumina carrier and metal alloy honeycomb substrate.
In the case of, according to the invention it is preferred to, the matrix can be selected from aluminium oxide, silica, amorphous silica-alumina, oxidation
At least one of zirconium, titanium oxide, boron oxide and alkaline earth oxide.
The catalyst of the present invention can be prepared according to various methods, as long as the catalysis of aforementioned claim of the present invention can be prepared
Agent, for the present invention, preferably catalyst of the invention is prepared as follows：(1) molecular sieve and aqueous solvent are mixed
And grind, molecular sieve pulp is obtained, the molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure；(2) will
The molecular sieve pulp is mixed with substrate source, forms active component coating slurries；(3) coated with the active component coating slurries
Ordered structure carrier and drying and roasting.
In the case of, according to the invention it is preferred to, activearm that the addition of the substrate source and the molecular sieve causes
Divide in coating, on the basis of the total weight of the active component coating, the content total amount of matrix is 5-50 weight %, and molecular sieve contains
It measures as 50-95 weight %.
In method provided by the invention, the matrix in the active component that the substrate source is prepared for offer, this hair
It is bright to this without particular/special requirement.It is worth noting that, when the matrix is silica and/or aluminium oxide, although the molecular sieve
In containing aluminium oxide and silica, but the silica and the amount of aluminium oxide that contain in the molecular sieve still can be regarded as the molecule
The amount of sieve, is not counted in silica and aluminium oxide.The content of each component in active component made from method i.e. provided by the present invention
It is calculated according to inventory.
According to the present invention, sieve particle diameter d in molecular sieve pulp described in step (1)90For 1-10 microns, it is preferably
5-10 microns, the solid content of the molecular sieve pulp is 15-70 weight %, and the aqueous solvent is deionized water.
In accordance with the present invention it is preferred that using the total weight of the active component coating slurries obtained in step (2) as base
Standard, the content of the molecular sieve is 3-60 weight %, and the total content for the substrate source counted using butt is 0.3-18 weight %.
According to the present invention, active component coating slurries described in step (2) can also contain dispersant, the dispersant with
The weight ratio of the molecular sieve is less than 0.2 and more than 0；Preferably 0.0005-0.015：1.
According to the present invention, dispersant described in step (2) in containing polyhydroxy, polyvinyl and polycarboxylic acids base extremely
A kind of few compound of group, such as one or more of polyethylene glycol, glycerine, polyvinyl alcohol or polyacrylic acid, preferably
For polyethylene glycol and/or polyacrylic acid.
According to the present invention, step (3) can by various painting methods by the active component coating grout distribution to rule
On the inner surface of whole structure carrier and/or outer surface, catalyst provided by the invention is prepared.The method of the coating can be water
Coating, infusion process or spray process.The method that the concrete operations of coating are referred to described in CN1199733C carries out.The coating
Temperature be preferably 10-70 DEG C, more preferably 15-35 DEG C, the pressure of coating is preferably -0.04 megapascal to 0.4 megapascal, during coating
Between be preferably 0.1-100 seconds.
According to the present invention, the ordered structure carrier for coating the good active component coating slurries is dried and roasted.
The method and condition of the drying are known to those skilled in the art, for example, dry method can be dried, dry, rousing
It air-dries dry.Under preferable case, in step (3), dry temperature can be room temperature to 300 DEG C, be preferably 100-200 DEG C；It is described
The dry time be at least 0.5 it is small when, be preferably 1-10 it is small when.
According to the present invention, the condition that is roasted described in step (3) or known to one of skill in the art, it is general come
It says, the temperature of the roasting is 400-800 DEG C, is preferably 500-700 DEG C；The time of the roasting be at least 0.5 it is small when, preferably
For 1-10 it is small when.
According to the present invention, the species of the molecular sieve has been described in foregoing, and details are not described herein.
According to the present invention, when the matrix be silica when, substrate source can be silica source, preferably described silica source
It is more than the natural crystal of 45 weight % for silica or silica content.Preferably, the silica source can be Ludox, layer
At least one of column clay, diatomite, expanded perlite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.
According to the present invention, when the matrix is aluminium oxide, substrate source can be alumina source, and the alumina source can be with
The substance of aluminium oxide can be changed under conditions of the roasting for step (3).Preferably, the alumina source is the thin water of plan
One or more in aluminium stone, hydrated alumina and Aluminum sol；The hydrated alumina is boehmite, the soft aluminium of a false water
At least one of stone, hibbsite and amorphous hydroted alumina.
The present invention also provides catalyst made from method provided by the present invention.
According to the present invention, which includes ordered structure carrier and is distributed in ordered structure inner surface of the carrier and/or outer
The active component coating on surface；On the basis of the total weight of the catalyst, the content of the active component coating is 10-50 weights
Measure %；On the basis of the total weight of the active component coating, the active component coating is total containing silica and aluminium oxide
Content is 5-50 weight %, and the content of molecular sieve is 50-95 weight %；The molecular sieve is with ten-ring two-dimensional elliptic type hole
The molecular sieve of road structure.Total content preferably containing silica and aluminium oxide is 5-20 weight %, and the content of molecular sieve is 80-
95 weight %.
The present invention also provides 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 with catalyst are contacted, obtain propylene product, wherein, the catalyst is the present invention
The catalyst of 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/oil feed weight ratio is 0.3-2, is preferably 0.4-1.7；Catalyst in terms of active component coating,
Naphtha feed weight (hourly) space velocity (WHSV) is 2-40h-1, it is preferably 2.3-36.5h-1。
In the case of, according to the invention it is preferred to, the naphtha contains the alkene of 0.5-1.5 weight %, 40-60 weight %
Alkane, the cycloalkane of 20-40 weight % 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 embodiment, using the instrument of agilent company HP6890 models
Device measures.Yield and selectivity are calculated by the following formula：
Yield=(purpose product (C2 =+C3 =) growing amount/reaction-ure feeding amount) × 100%
Selectivity=(purpose product (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.By 56.2 grams of ZSM-35 molecular sieves (Nanjing Ji Cang nanosecond science and technology Co., Ltd, Si/Al moles
Than=30：1) mixed with 56.2 grams of deionized waters, wet ball grinding is into molecular sieve pulp, sieve particle diameter d90=10 microns,
Solid content is 50 weight %.28.4 grams of Aluminum sols (salic 22 weight %, sinopec catalyst Shandong point are added in slurries
Company produces), it stirs 10 minutes, adds in 1.5 grams of the polyglycol solution (weight percent of polyethylene glycol in polyglycol solution
For 2 weight %), stirring obtains catalyst coat slurries (coating slurry) in 20 minutes.
By active component coating slurries, (carrier hole density is 100 holes/square centimeter to coating cordierite honeycomb carrier, each
The sectional area in hole is 7 square millimeters, percent opening 80%, and the shape in hole is square), at 120 DEG C it is dry 5 it is small when and 500 DEG C
It is lower roasting 5 it is small when, obtain catalyst, wherein, active component coating content be 15 weight %.
Active component coating composition is calculated by feeding intake：ZSM-35 molecular sieve content is 90 weight %, and matrix (aluminium oxide) contains
It measures as 10 weight %.
(2) propylene is produced.By catalyst made from (1) as catalyst bed, monolithic reactors are formed, wherein, it is living
Property component coating total weight be 62.5 grams.By naphtha (1 weight % of olefin-containing, containing 56 weight % of alkane, containing 32 weight of cycloalkane
Measure %, containing 11 weight % of aromatic hydrocarbons, 0.5 μ g/g of basic nitrogen) and water inject above-mentioned monolithic reactors after 250 DEG C preheat.Its
In, the weight (hourly) space velocity (WHSV) total weight of active component coating (weight of naphtha compared with) of naphtha injection is 2.3hr-1, water/oil
Feed weight ratio is 0.46.Reaction temperature is 520 DEG C, pressure 0.1MPa.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.By 32 grams of Ferrierite zeolite powders (self-control, Si/Al molar ratio=50：1) with 20 grams
Deionized water mixes, and wet ball grinding is into slurries, sieve particle diameter d in slurries90=8 microns；150 grams of glue are added in slurries
Molten boehmite (salic 18 weight %, pH value 2.8, sinopec catalyst asphalt in Shenli Refinery product) stirs 15 points
Clock；3.2 grams of polyacrylic acid solution (polyacrylic acid weight percent is 1 weight % in polyacrylic acid solution) is added in, stirs 30 points
Clock obtains catalyst coat slurries.
By active component coating slurries, (carrier hole density is 80 holes/square centimeter to coating cordierite honeycomb carrier, each
The sectional area in hole is 5 square millimeters, percent opening 60%, and the shape in hole is circle), at 120 DEG C it is dry 5 it is small when and 500 DEG C at
Roast 5 it is small when, obtain catalyst, wherein, active component coating content be 20 weight %.
Active component coating composition is calculated by feeding intake：Ferrierite zeolite contents be 54 weight %, matrix (aluminium oxide)
Content is 46 weight %.
(2) propylene is produced.By catalyst made from (1) as catalyst bed, monolithic reactors are formed, wherein, it is living
Property component coating total weight be 59 grams.By naphtha (1 weight % of olefin-containing, containing 56 weight % of alkane, containing 32 weight of cycloalkane
Measure %, containing 11 weight % of aromatic hydrocarbons, 0.4 μ g/g of basic nitrogen) and water inject above-mentioned monolithic reactors after 250 DEG C preheat.Its
In, the weight (hourly) space velocity (WHSV) total weight of active component coating (weight of naphtha compared with) of naphtha injection is 36.5hr-1, water/
Oily feed weight ratio is 0.96.Reaction temperature is 570 DEG C, pressure 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 70 grams of ZSM-57 zeolites (self-control, Si/Al molar ratio=80：1) mixed with 60 grams of distilled water
It closes, wet ball grinding is into slurries, sieve particle diameter d in slurries90=5 microns；143 grams of acidic silicasols are added in slurries
(21 weight % of silicon oxide-containing, sinopec catalyst asphalt in Shenli Refinery product) stirs 60 minutes；Add in polyethylene glycol and polypropylene
Sour 12.6 grams of mixed solution (polyethylene glycol and polyacrylic acid weight percent be respectively 3 weight % and 5 weight %), stirs 30 points
Clock obtains catalyst coat slurries.
By active component coating slurries, (carrier hole density is 20 holes/square centimeter to coating cordierite honeycomb carrier, each
The sectional area in hole is 2 square millimeters, percent opening 75%, and the shape in hole is circle), at 120 DEG C it is dry 5 it is small when and 500 DEG C at
Roast 5 it is small when, obtain catalyst, wherein, active component coating content be 30 weight %.
Active component coating composition is calculated by feeding intake：ZSM-57 zeolite contents be 70 weight %, matrix (silica) content
For 30 weight %.
(2) propylene is produced.By catalyst made from (1) as catalyst bed, monolithic reactors are formed, wherein, it is living
Property component coating total weight be 100 grams.By naphtha (1 weight % of olefin-containing, containing 56 weight % of alkane, containing 32 weight of cycloalkane
Measure %, containing 11 weight % of aromatic hydrocarbons, 0.6 μ g/g of basic nitrogen) and water inject above-mentioned monolithic reactors after 250 DEG C preheat.Its
The weight (hourly) space velocity (WHSV) total weight of active component coating (weight of naphtha compared with) of middle naphtha injection is 4.6hr-1, water/oil
Feed weight ratio is 1.61.Reaction temperature is 590 DEG C, pressure 0.2MPa.Reaction result is shown in Table 1.
Embodiment 4
According to the method cracking naphtha of embodiment 3, the difference is that, molecular sieve is by ZSM-35 zeolite (sial in catalyst
30) atomic molar ratio with COK-5 zeolites (sial atomic molar ratio is by 50) by replacing, and the weight ratio of the two is 1:1.
Embodiment 5
According to the method cracking naphtha of embodiment 3, the difference is that, molecular sieve is by Ferrierite zeolites in catalyst
(sial atomic molar ratio is by 50) and ZSM-57 zeolites (sial atomic molar ratio is by 80) replace, and the weight ratio of the two is 2:
1。
Embodiment 6
According to the method cracking naphtha of embodiment 3, the difference is that, (sial is former by FU-9 zeolites for molecular sieve in catalyst
50) sub- molar ratio with ZSM-57 zeolites (sial atomic molar ratio is by 30) by replacing, and the weight ratio of the two is 5:1.
Embodiment 7
According to the method cracking naphtha of embodiment 4, unlike, in catalyst in molecular sieve ZSM-35 zeolites by ZSM-
The mixture of 35 zeolites (sial atomic molar ratio is by 30) and Ferrierite zeolites (sial atomic molar ratio is by 30) replaces, and two
The weight ratio of person is 3:1；COK-5 zeolites are by ZSM-57 zeolites (sial atomic molar ratio is 50) and COK-5 zeolites (sial atom
Molar ratio is replaced by mixture 50), and the weight ratio of the two is 4:1.
Comparative example 1
(1) catalyst is prepared.By 56.2 grams of ZSM-5 zeolites, (Nankai University produces, Si/Al molar ratio=30：1) with 56.2
The mixing of gram deionized water, wet ball grinding is into molecular sieve pulp, sieve particle diameter d90=10 microns, solid content is 50 weights
Measure %.28.4 grams of Aluminum sols (salic 22 weight %, sinopec catalyst asphalt in Shenli Refinery produce) are added in slurries, are stirred
It mixes 20 minutes and obtains mix slurry through extruded moulding.
Active component coating composition is calculated by feeding intake：ZSM-5 zeolite content is 90 weight %, and matrix (aluminium oxide) content is
10 weight %.
(2) propylene is produced.By catalyst made from (1) as catalyst bed, fixed bed reactors are formed.By naphtha
(1 weight % of olefin-containing, containing 56 weight % of alkane, containing 32 weight % of cycloalkane, containing 11 weight % of aromatic hydrocarbons, 0.5 μ g/g of basic nitrogen)
With water above-mentioned fixed bed reactors are injected after 250 DEG C of preheatings.Wherein the weight (hourly) space velocity (WHSV) of naphtha injection is (compared with catalyst bed
The total weight of layer) it is 4.6hr-1, water/oil feed weight ratio is 1.61.Reaction temperature is 590 DEG C, pressure 0.1MPa.Reaction knot
Fruit is shown in Table 1.
Comparative example 2
According to the method for embodiment 1, the difference is that, the catalyst used is the ZSM-35 zeolite (silicon containing 18 weight %
Aluminium atom molar ratio is the bar shaped catalysis that 30) and the particle diameter of the matrix of 82 weight % (aluminium oxide) is 2mm, length is 5mm
Agent.
Calculate (C2 =+C3 =) yield and (C2 =~C4 =) selectivity, the results are shown in Table 1.
Comparative example 3
According to the method for embodiment 1, the difference is that, the molecules of active components of active component coating in ordered structure catalyst
It sieves as Beta zeolites (sial atomic molar ratio is 30), remaining all same.
Calculate (C2 =+C3 =) yield and (C2 =~C4 =) selectivity, the results are shown in Table 1.
Table 1
From the data result of table 1 can be seen that catalyst provided by the invention using ordered structure carrier and containing with
Ten-ring two-dimensional elliptic type pore passage structure is a kind of active component coating of FER or MFS structures, is carrying out naphtha catalysis
In cracking production propylene, high ethylene and propene yield can be obtained, and wherein propylene/ethylene ratio is more than 1, can realize fecund
Propylene.
Claims (16)
1. a kind of catalyst of naphtha catalytic cracking production propylene, the catalyst include：Ordered structure carrier and be distributed in it is regular
Structure carrier inner surface and/or the active component coating of outer surface；On the basis of the total weight of the catalyst, the activearm
The content for dividing coating is 10-50 weight %；On the basis of the total weight of the active component coating, the active component coating contains
There are the molecular sieve of 50-95 weight % and the matrix of 5-50 weight %；The molecular sieve is with ten-ring two-dimensional elliptic type hole road
The molecular sieve of structure, the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure are tied for the molecular sieve of FER structures with MFS
The mixture of the molecular sieve of structure, wherein, the weight ratio of the molecular sieve of FER structures and the molecular sieve of MFS structures is 0.1-10:1.
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 1-5:1；
The molecular sieve of the FER structures is ZSM-35 zeolites, Ferrierite zeolites, FU-9 zeolites, ISI-6 zeolites, NU-23 boiling
At least one of stone and Sr-D zeolites；The molecular sieve of MFS structures is at least one of ZSM-57 zeolites and COK-5 zeolites.
3. catalyst according to claim 1, wherein, the molecular sieves of the FER structures is ZSM-35 zeolites,
One kind in Ferrierite zeolites and FU-9 zeolites.
4. catalyst according to claim 2, 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 ZSM-57 zeolites and the mixture of COK-5 zeolites.
5. according to the catalyst described in any one in claim 1-4, wherein, using the total weight of the active component coating as
Benchmark, the active component coating contain the molecular sieve of 54-90 weight % and the matrix of 10-46 weight %.
6. according to the catalyst described in any one in claim 1-4, wherein, on the basis of the total weight of the catalyst,
The content of the active component coating is 15-30 weight %.
7. catalyst according to claim 1, wherein, the ordered structure carrier is selected from the parallel hole with both ends open
The monolithic substrate of road structure.
8. catalyst according to claim 7, wherein, the hole density in the section of the ordered structure carrier for 6-140 holes/
Square centimeter, the sectional area in each hole is 0.4-10 square millimeters, percent opening 50-80%.
9. according to the catalyst described in any one in claim 1,7 and 8, wherein, it is blue or green that the ordered structure carrier is selected from violet
At least one of stone honeycomb substrate, mullite honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrate.
10. catalyst according to claim 1, wherein, the matrix is selected from aluminium oxide, silica, amorphous silica-alumina, oxygen
Change at least one of zirconium, titanium oxide, boron oxide and alkaline earth oxide.
11. a kind of side for the catalyst for preparing the naphtha catalytic cracking production propylene in claim 1-10 described in any one
Method, this method include：
(1) molecular sieve and aqueous solvent are mixed and ground, obtain molecular sieve pulp；
(2) molecular sieve pulp with substrate source is mixed, forms active component coating slurries；
(3) with active component coating slurries coating ordered structure carrier and drying and roasting.
12. the method according to claim 11, wherein, in step (1), sieve particle diameter in the molecular sieve pulp
d90For 1-10 microns, the solid content of the molecular sieve pulp is 15-70 weight %, and the aqueous solvent is deionized water.
13. according to the method for claim 11, wherein, in step (2), the active component coating slurries are also containing scattered
The weight ratio of agent, the dispersant and the molecular sieve is less than 0.2 and more than 0.
14. the catalyst as made from the method described in any one in claim 11-13.
15. a kind of method of naphtha catalytic cracking production propylene, this method include：Under naphtha catalytic cracking reaction condition,
Naphtha and water with catalyst are contacted, obtain propylene product, which is characterized in that the catalyst include claim 1-10 and
Catalyst in 14 described in any one.
16. according to the method for claim 15, wherein, the naphtha catalytic cracking reaction condition includes：Temperature is
520-590 DEG C, pressure 0.1-0.2MPa, water/oil feed weight ratio is 0.3-2；Catalyst is in terms of active component coating, stone brain
Oil charging weight (hourly) space velocity (WHSV) is 2-40h-1。
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| CN1903808A (en) * | 2005-07-28 | 2007-01-31 | 中国石油化工股份有限公司 | Method of preparing propylene by olefine containing gasoline catalytic cracking |
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|---|---|---|---|---|
| US7326332B2 (en) * | 2003-09-25 | 2008-02-05 | Exxonmobil Chemical Patents Inc. | Multi component catalyst and its use in catalytic cracking |
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| CN1152261A (en) * | 1994-07-08 | 1997-06-18 | 埃克森化学专利公司 | Molecular sieves and processes for their manufacture |
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