CN105582993B - 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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- CN105582993B CN105582993B CN201410562100.3A CN201410562100A CN105582993B CN 105582993 B CN105582993 B CN 105582993B CN 201410562100 A CN201410562100 A CN 201410562100A CN 105582993 B CN105582993 B CN 105582993B
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Abstract
Catalyst the present invention provides a kind 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 contains the first molecular sieve, the second molecular sieve and third molecular sieve, first molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, second molecular sieve is the molecular sieve with twelve-ring pore passage structure, and the third molecular sieve is small pore molecular sieve of the maximum duct opening diameter in below 0.45nm.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 3.
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 are difficult to meet demand, therefore develop 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 a large amount 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 the Intergrown molecular of the coexisting molecular sieve of ZSM-5 and modenite, ZSM-5 and β zeolites
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.
Invention content
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 catalysis
Agent includes ordered structure carrier and the active component coating for being distributed in ordered structure inner surface of the carrier and/or outer surface；With described
On the basis of the total weight of catalyst, the content of the active component coating is 10-50 weight %；With the active component coating
On the basis of total weight, the active component coating contains the molecular sieve of 50-95 weight % and the matrix of 5-50 weight %；Described point
For son sieve containing the first molecular sieve, the second molecular sieve and third molecular sieve, first molecular sieve is with ten-ring two-dimensional elliptic
The molecular sieve of type pore passage structure, second molecular sieve be the molecular sieve with twelve-ring pore passage structure, the third molecule
Sieve the small pore molecular sieve in below 0.45nm for maximum duct opening diameter.
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；
(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；
Wherein, the molecular sieve contains the first molecular sieve, the second molecular sieve and third molecular sieve, and first molecular sieve is
Molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, second molecular sieve are point with twelve-ring pore passage structure
Son sieve, the third molecular sieve are small pore molecular sieve of the maximum duct opening diameter in below 0.45nm.
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 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 3.
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 understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict 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 cellular set of the carrier with ordered structure
Body；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 contains the first molecule
Sieve, the second molecular sieve and third molecular sieve, first molecular sieve are the molecule with ten-ring two-dimensional elliptic type pore passage structure
Sieve, second molecular sieve are the molecular sieve with twelve-ring pore passage structure, and the third molecular sieve is maximum channel openings
Diameter is in the small pore molecular sieve of below 0.45nm.
In regular catalyst provided by the invention, it is used as and is urged using the first molecular sieve, the second molecular sieve and third molecular sieve
Change lytic activity component, the yield of higher naphtha catalytic cracking production propylene can be obtained.
According to a preferred embodiment of the present invention, three layers during the active component coating is including inside and outside, wherein, it is interior
Layer contains second molecular sieve containing the third molecular sieve, outer layer, and first molecular sieve is contained in middle level；It is further preferred that with
The matrix of internal layer active component coating total weight, the third molecular sieve containing 50-95 weight % and 5-50 weight %；With outer layer
The matrix of active component coating total weight, the second molecular sieve containing 50-95 weight % and 5-50 weight %；With middle level activity
The matrix of component total coating weight meter, the first molecular sieve containing 50-95 weight % and 5-50 weight %.
Wherein, internal layer refers to the layer contacted with ordered structure carrier peripheral wall；Outer layer refers to the layer arranged extruded on internal layer,
Close to pipeline center, and middle level is between internal layer and outer layer.
For preferred internal layer coating using third molecular sieve as catalytic cracking activity component, middle layer uses first in the present invention
Molecular sieve is as catalytic cracking activity component, and outer layer uses the second molecular sieve as lytic activity component, and respectively by first
Molecular sieve, the second molecular sieve and third molecular sieve and matrix are made active component coating and are distributed on ordered structure carrier, are formed
Ordered structure catalyst can obtain the yield of higher naphtha catalytic cracking production propylene.
According to the present invention, first molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, preferably
Channel openings diameter is at 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 mixing of first molecular sieve for the molecular sieve of FER structures and the molecular sieve of MFS structures
Object.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 first molecular sieve can be 0.1-100：1；Preferably
30-80:1。
In accordance with the present invention it is preferred that the channel openings of second molecular sieve are 0.6-0.75 nanometers a diameter of.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 molecular sieve of MOR, OFF and SAO structure.It is particularly preferred that second molecular sieve for Beta, SAPO-5,
At least one of 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 accordance with the present invention it is preferred that the third molecular sieve is selected from ATT, ATN, CHA, ITE, STI, WEN structure
At least one of molecular sieve.It is highly preferred that the third molecular sieve is at least one in ITQ-3, SAPO-34 and cancrinite
Kind.
In the case of, according to the invention it is preferred to, first molecular sieve, second molecular sieve and the third molecular sieve
Weight ratio is 0.1-15：0.1-5：1, preferably 1-14：0.5-3：1.
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 60-85 weight % and the matrix of 15-40 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
15-40 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 trepanning
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, preferably 20-100 holes/square centimeter；The sectional area in each hole is 0.4-10 square millimeters, 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 wave
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 purpose of the present invention can be achieved in the catalyst for meeting aforementioned claim of the present invention, and the present invention is to preparation method without spy
Different requirement, according to a preferred embodiment of the present invention, the catalyst is prepared as follows：(1) by molecular sieve and
Aqueous solvent is mixed and is ground, and obtains 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；
Wherein, the molecular sieve contains the first molecular sieve, the second molecular sieve and third molecular sieve, and first molecular sieve is
Molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, second molecular sieve are point with twelve-ring pore passage structure
Son sieve, the third molecular sieve are small pore molecular sieve of the maximum duct opening diameter in below 0.45nm.
A kind of preferred embodiment according to the present invention, method of the invention prepare catalyst as follows：(1)
First molecular sieve, the second molecular sieve, third molecular sieve are respectively mixed and ground with aqueous solvent, obtains the first molecule screening the pulp
Liquid, the second molecular sieve pulp and third molecular sieve pulp；
(2) the first molecular sieve pulp, the second molecular sieve pulp and third molecular sieve pulp respectively with substrate source are mixed, obtained
To the first active component coating slurries, the second active component coating slurries and third active component coating slurries；
(3) ordered structure carrier is coated with the third active component coating slurries, then dry roasting is lived with first
Property the coating of component coating slurry the ordered structure carrier of third active component coating, dry roasting is distributed with；Then with second
Active component coating slurries coat the ordered structure carrier that third active component coating and the first active component coating is distributed with, and do
It is roasted after dry.
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 of matrix is 5-50 weight %, and the content of molecular sieve is
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, such as 5-
10 microns, the solid content of the molecular sieve pulp is 15-70 weight %, such as 30-65 weight %, the aqueous solvent are water example
Such as deionized water.
According to a preferred embodiment of the present invention, the first molecular sieve pulp, the second molecular sieve described in step (1)
The sieve particle diameter d of slurries and third molecular sieve pulp90Respectively 1-10 microns, such as 5-10 microns, described first point
The solid content of sub- screening the pulp liquid, the second molecular sieve pulp and third molecular sieve pulp is respectively 15-70 weight %, such as 30-65 weights
% is measured, the aqueous solvent is water such as 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 are 3-60 weight %, preferably 15-45 weight %, total content of the substrate source in terms of matrix
For 0.3-18 weight %, preferably 1-15 weight %.
According to a preferred embodiment of the present invention, with the first active component coating slurries, the second activearm
On the basis of point coating slurry, the respective total weight of third active component coating slurries, first molecular sieve (or the second molecular sieve
Or third molecular sieve) content be respectively 3-60 weight %, preferably 15-45 weight %, the substrate source is total in terms of matrix
Content is 0.3-18 weight %, preferably 1-15 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 0.0001-0.005：1.
A preferred embodiment of the invention, described in step (2) described in the first active component coating slurries
The weight ratio of dispersant and first molecular sieve is 0.0001-0.004：1, described in the second active component coating slurries point
The weight ratio of powder and second molecular sieve is 0.0001-0.0005：1, described in the third active component coating slurries point
The weight ratio of powder and the third molecular sieve is 0.0002-0.0004：1.
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, for example, it is one or more in 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 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 is 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, preferably 100-200 DEG C；It is described
The dry time is at least 0.5 hour, preferably 1-10 hours.
According to the present invention, the condition roasted described in step (3) may be known to one of skill in the art, generally come
It says, the temperature of the roasting is 400-800 DEG C, preferably 500-700 DEG C；The time of the roasting is at least 0.5 hour, preferably
It is 1-10 hours.
According to the present invention, the type of the molecular sieve has been described in aforementioned, and details are not described herein.
According to the present invention, when the matrix is silica, 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 laminated clay column,
At least one of diatomite, expanded perlite, silicalite, Ludox, 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 hydration oxygen
Change one or more in aluminium, Aluminum sol and boehmite；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, 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 contains the first molecule
Sieve, the second molecular sieve and third molecular sieve, first molecular sieve are the molecule with ten-ring two-dimensional elliptic type pore passage structure
Sieve, second molecular sieve are the molecular sieve with twelve-ring pore passage structure, and the third molecular sieve is maximum channel openings
Diameter is in the small pore molecular sieve of below 0.45nm.
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 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/oil feed weight ratio is 0.3-2, and catalyst is in terms of active component coating, when naphtha feed is heavy
Air speed is 2-40h-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 =) production quantity/reaction-ure feeding amount) × 100%
Selectivity=(purpose product (C2 =~C4 =) production quantity/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 10 grams of SAPO-34 molecular sieves (Tianjin Chemist Technology Development Co., Ltd, Si/Al
Molar ratio=0.25：1) it is mixed with 10 grams of deionized waters, for wet ball grinding into molecular sieve pulp, sieve particle diameter d90=8 is micro-
Rice, solid content are 50 weight %.3 grams of Aluminum sols (salic 22 weight %, sinopec catalyst Shandong point are added in slurries
Company produces), it stirs 10 minutes, adds in 0.5 gram of polyglycol solution (polyglycol solution weight percent is 2 weight %),
Stirring obtains catalyst coat for 20 minutes and prepares mix slurry (coating slurry) 1.
By active component coating slurries 1, (carrier hole density is 100 holes/square centimeter to coating cordierite honeycomb carrier, often
The sectional area in a hole is 7 square millimeters, percent opening 80%, and the shape in hole is square), dry 5 hours and 500 at 120 DEG C
It is roasted 5 hours at DEG C, obtains catalyst precarsor 1, wherein internal layer active component coating content is 3 weight %.
By 50 grams of ZSM-35 molecular sieves (Shanghai Zhuo Yue Chemical Co., Ltd.s, Si/Al molar ratio=60：1) with 50 grams go from
The mixing of sub- water, wet ball grinding into molecular sieve pulp, d90=10 micron of sieve particle diameter, solid content be 50 weight %.It is starching
56.8 grams of Aluminum sols (salic 22 weight %, sinopec catalyst asphalt in Shenli Refinery produce) are added in liquid, are stirred 10 minutes,
1.5 grams of polyglycol solution (polyglycol solution weight percent is 2 weight %) is added in, stirring obtains catalyst painting for 20 minutes
Layer prepares mix slurry (coating slurry) 2.
By active component coating slurries 2, coat at 1,120 DEG C of catalyst precarsor that roasting 5 is small at dry 5 hours and 500 DEG C
When, catalyst precarsor 2 is obtained, wherein, middle level active component coating content is 18 weight %.
By 30 grams of Beta molecular sieves (self-control, Si/Al molar ratio=50：1) mixed with 30 grams of deionized waters, wet ball grinding into
Molecular sieve pulp, d90=10 microns of sieve particle diameter, solid content are 50 weight %.It is molten that 16.8 grams of aluminium are added in slurries
Glue (salic 22 weight %, sinopec catalyst asphalt in Shenli Refinery produce), stirs 10 minutes, adds in polyglycol solution
1.0 grams (polyglycol solution weight percent is 2 weight %), stirring obtains catalyst coat for 20 minutes and prepares mix slurry
3 (coating slurries).
By active component coating slurries 3, coat at 2,120 DEG C of catalyst precarsor that roasting 5 is small at dry 5 hours and 500 DEG C
When, wherein, outer layer active component coating content is 10 weight %.Active component coating composition is calculated by always feeding intake：Molecular sieve contains
It measures as 85 weight %, matrix (aluminium oxide) content is 15 weight %.
(2) propylene is produced.By catalyst made from (1) as catalyst bed, monolithic reactors are formed, wherein activity
The total weight of component coating is 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) (relative to total weight of active component coating) of naphtha injection is 25hr-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 30 grams of ITQ-3 molecular sieves (Si/Al molar ratio=10：1) it is mixed with 60 grams of deionized waters,
Wet ball grinding is into molecular sieve pulp, d90=8 microns of sieve particle diameter, and solid content is 33.3 weight %.It is added in slurries
10 grams of Ludox (21 weight % of silicon oxide-containing, sinopec catalyst asphalt in Shenli Refinery produce), stir 10 minutes, add in polypropylene
4.5 grams of acid solution (polyacrylic acid solution weight percent is 1 weight %), stirring obtains catalyst coat for 30 minutes and prepares mixing
Object slurries (coating slurry) 1.
By active component coating slurries 1, (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 at dry 5 hours and 500 DEG C
Roasting 5 hours, obtains catalyst precarsor 1, wherein, internal layer active component coating content is 10 weight %.
By 32 grams of Ferrierite zeolite molecular sieves (molecular sieve international corporation Zeolyst International, Si/Al
Molar ratio=10：1) it is mixed with 20 grams of deionized waters, wet ball grinding is into slurries, and sieve particle diameter d90=8 is micro- in slurries
Rice；150 grams of peptization boehmites are added in slurries, and (salic 18 weight %, pH value 2.8, sinopec catalyst are neat
Shandong branch company product), it stirs 15 minutes；Adding in 3.2 grams of polyacrylic acid solution, (polyacrylic acid solution weight percent is 1 weight
Measure %), polyacrylic acid solution addition is 10 weight % of molecular sieve, is stirred 30 minutes, obtains catalyst coat mixing
Object slurries 2.
By active component coating slurries 2, coat at 1,120 DEG C of catalyst precarsor that roasting 5 is small at dry 5 hours and 500 DEG C
When, catalyst precarsor 2 is obtained, wherein, middle level active component coating content is 10 weight %.
By 32 grams of mordenite molecular sieves (Shanghai Shen Tan environmental friendly materials Co., Ltd, Si/Al molar ratio=80：1) with
The mixing of 30 grams of deionized waters, wet ball grinding into molecular sieve pulp, d90=10 micron of sieve particle diameter, solid content be 50 weights
Measure %.122 grams of Aluminum sols (salic 22 weight %, sinopec catalyst asphalt in Shenli Refinery produce) are added in slurries, are stirred
It mixes 10 minutes, adds in 1.0 grams of polyglycol solution (polyglycol solution weight percent is 2 weight %), stirring obtains for 20 minutes
Mix slurry 3 (coating slurry) is prepared to catalyst coat.
By active component coating slurries 3, coat at 2,120 DEG C of catalyst precarsor that roasting 5 is small at dry 5 hours and 500 DEG C
When, wherein, outer layer active component coating content is 18 weight %.Active component coating composition is calculated by feeding intake：Molecular sieve content
For 63 weight %, matrix content is 37 weight %.
(2) propylene is produced.By catalyst made from (1) as catalyst bed, monolithic reactors are formed, wherein activity
The total weight of component coating is 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
The weight (hourly) space velocity (WHSV) (relative to total weight of active component coating) of middle naphtha injection is 36.5hr-1, water/oil 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 5 grams of cancrinites (Kai Long mining industry Co., Ltd, Si/Al molar ratio=3：1) with 7 grams go from
The mixing of sub- water, wet ball grinding into molecular sieve pulp, d90=5 micron of sieve particle diameter, solid content be 41.7 weight %.
2 grams of Ludox (21 weight % of silicon oxide-containing, sinopec catalyst asphalt in Shenli Refinery produce) are added in slurries, are stirred 10 minutes,
0.5 gram of polyglycol solution (polyglycol solution weight percent is 2 weight %) is added in, stirring obtains catalyst painting for 30 minutes
Layer prepares mix slurry (coating slurry) 1.
By active component coating slurries 1, (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 at dry 5 hours and 500 DEG C
Roasting 5 hours, obtains catalyst precarsor 1, wherein, internal layer active component coating content is 5 weight %.
By 70g ZSM-57 molecular sieves (Si/Al molar ratio=80：1) mixed with 60 grams of distilled water, wet ball grinding into slurries,
D90=5 microns of sieve particle diameter in slurries；Added in slurries 143 grams of acidic silicasols (21 weight % of silicon oxide-containing,
Sinopec catalyst asphalt in Shenli Refinery product), it stirs 60 minutes；Add in 12.6 grams of polyethylene glycol and polyacrylic acid mixed solution
(polyethylene glycol and polyacrylic acid weight percent are divided into 3 weight % and 5 weight %), stirring obtain catalyst coat system in 30 minutes
Standby mix slurry 2.
By active component coating slurries 2, coat at 1,120 DEG C of catalyst precarsor that roasting 5 is small at dry 5 hours and 500 DEG C
When, catalyst precarsor 2 is obtained, wherein, middle level active component coating content is 20 weight %.
By 10 grams of SSZ-13 molecular sieves (Si/Al molar ratio=40：1) it is mixed with 10 grams of deionized waters, wet ball grinding ingredient
Sub- screening the pulp liquid, d90=10 microns of sieve particle diameter, solid content are 50 weight %.20 grams of Ludox are added in slurries (to contain
21 weight % of silica, sinopec catalyst asphalt in Shenli Refinery produce), it stirs 10 minutes, adds in 1.0 grams of polyglycol solution
(polyglycol solution weight percent is 2 weight %), stirring obtains catalyst coat for 20 minutes and prepares (the painting of mix slurry 3
Layer slurries).
By active component coating slurries 3, coat at 2,120 DEG C of catalyst precarsor that roasting 5 is small at dry 5 hours and 500 DEG C
When, wherein, outer layer active component coating content is 5 weight %.
Active component coating composition is calculated by feeding intake：Molecular sieve content is 71 weight %, and matrix (silica) content is 29
Weight %.
(2) propylene is produced.By catalyst made from (1) as catalyst bed, monolithic reactors are formed, wherein activity
The total weight of component coating is 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) (relative to total weight of active component coating) 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, in catalyst, the first molecular sieve is by ZSM-35 zeolites
(sial atomic molar ratio is by 30) and COK-5 zeolites (sial atomic molar ratio is by 50) replace, 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, in catalyst, the first molecular sieve is by Ferrierite
Zeolite (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
It 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 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 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)
It replaces, 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 molar ratio is replaced by mixture 50), and the weight ratio of the two is 4:1.
Embodiment 8
It is carried out according to the method for embodiment 3, unlike, the first active component coating slurries, the second active component are applied
Coating ordered structure carrier is carried out after layer slurries and the mixing of third active component coating slurries, is then dried and roasts, do
Dry and roasting temperature is same as Example 3, dry and roasting after coating dry total time and the total time of roasting and embodiment 3
The total time of burning is identical, remaining condition all same.
Embodiment 9
It is carried out according to the method for embodiment 3, unlike, first regular knot is coated with the second active component coating slurries
Structure carrier, then be dried and roast, it is then coated with the first active component coating slurries, is then dried and roasts
It burns, is then coated with third active component coating slurries, be then dried and roast, dry and roasting temperature and embodiment
3 is identical, remaining condition all same.
Comparative example 1
According to the method for embodiment 1, unlike, ZSM-35 molecular sieve, SAPO-34 molecular sieves by equivalent Beta zeolites
Instead of i.e. all second molecular sieves of molecular sieve.
Comparative example 2
According to the method for embodiment 1, unlike, Beta zeolites, SAPO-34 molecular sieves by equivalent ZSM-35 molecular sieve
Instead of i.e. all first molecular sieves of molecular sieve.
Comparative example 3
According to the method for embodiment 1, unlike, Beta zeolites, ZSM-35 molecular sieve by equivalent SAPO-34 molecular sieves
Instead of i.e. all third molecular sieves of molecular sieve.
Comparative example 4
It is carried out according to the method for embodiment 3, unlike, the catalyst used is prepared as follows：
By 50 grams of ZSM-5 molecular sieves, (Nankai University produces, Si/Al molar ratio=30：1) it is mixed with 50 grams of deionized waters,
Wet ball grinding is into molecular sieve pulp, d90=10 microns of sieve particle diameter, and solid content is 50 weight %.It is added in slurries
56.8 grams of Aluminum sols (salic 22 weight %, sinopec catalyst asphalt in Shenli Refinery produce), stirring is mixed for 20 minutes
Object slurries are through extruded moulding.
Active component coating composition is calculated by feeding intake：ZSM-5 molecular sieve content be 80 weight %, matrix (aluminium oxide) content
For 20 weight %.
Table 1
It can be seen that in a preferred embodiment of the invention from the data result of table 1, catalyst provided by the invention is adopted
With ordered structure carrier and three layers of active component coating；Wherein, internal layer molecular sieve is maximum duct opening diameter at 0.45 nanometer
Following third molecular sieve, middle layer molecular sieve be the first molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, outer layer
Molecular sieve is the molecular sieve with twelve-ring pore passage structure.In naphtha catalytic cracking production propylene is carried out, height can be obtained
Ethylene and propene yield, and wherein propylene/ethylene ratio be more than 3, can realize producing more propylene.
Claims (20)
1. a kind of catalyst of naphtha catalytic cracking production propylene, the catalyst include ordered structure carrier and are distributed in regular knot
Structure inner surface of the carrier and/or the active component coating of outer surface；On the basis of the total weight of the catalyst, the active component
The content of coating is 10-50 weight %；On the basis of the total weight of the active component coating, the active component coating contains
The molecular sieve of 50-95 weight % and the matrix of 5-50 weight %；The molecular sieve contains the first molecular sieve, the second molecular sieve and
Type three-molecular screen alternating, first molecular sieve be the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, second molecular sieve
For the molecular sieve with twelve-ring pore passage structure, the third molecular sieve is maximum duct opening diameter below 0.45nm's
Small pore molecular sieve, the active component coating include it is inside and outside in three layers, wherein, internal layer contains the third molecular sieve, and outer layer contains
There is second molecular sieve, first molecular sieve is contained in middle level.
2. catalyst according to claim 1, wherein, with internal layer active component coating total weight, contain 50-95 weights
Measure the third molecular sieve of % and the matrix of 5-50 weight %；With outer layer active component coating total weight, contain 50-95 weight %
The second molecular sieve and 5-50 weight % matrix；With middle level active component coating total weight, containing 50-95 weight %
The matrix of one molecular sieve and 5-50 weight %.
3. catalyst according to claim 1 or 2, wherein, first molecular sieve, the second molecular sieve and third molecular sieve
Weight ratio be 0.1-15：0.1-5：1.
4. catalyst according to claim 1 or 2, wherein, first molecular sieve, the second molecular sieve and third molecular sieve
Weight ratio be 1-14：0.5-3：1.
5. catalyst according to claim 1 or 2, wherein,
First molecular sieve is the molecular sieve of FER structures and/or the molecular sieve of MFS structures, the molecular sieve of the FER structures are
At least one of ZSM-35 zeolites, Ferrierite zeolites, FU-9 zeolites, ISI-6 zeolites, NU-23 zeolites and Sr-D zeolites；
The molecular sieve of MFS structures is at least one of ZSM-57 zeolites and COK-5 zeolites；
The channel openings of second molecular sieve are 0.6-0.75 nanometers a diameter of；
The third molecular sieve is selected from least one of molecular sieve with ATT, ATN, CHA, ITE, STI and WEN structure.
6. catalyst according to claim 5, wherein, first molecular sieve is the molecular sieve and MFS of the FER structures
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.
7. catalyst according to claim 6, wherein, the weight ratio of the molecular sieve of FER structures and the molecular sieve of MFS structures
For 1-5:1.
8. catalyst according to claim 5, wherein, the molecular sieves of the FER structures is ZSM-35 zeolites,
One kind in Ferrierite zeolites and FU-9 zeolites.
9. catalyst according to claim 5, 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.
10. catalyst according to claim 5, wherein, second molecular sieve be selected from AET, AFR, AFS,
At least one of molecular sieve of AFI, BEA, BOG, CFI, CON, GME, IFR, ISV, LTL, MEI, MOR, OFF and SAO structure.
11. catalyst according to claim 1 or 2, wherein, on the basis of the total weight of the active component coating, institute
Molecular sieve that active component coating contains 60-85 weight % and the matrix of 15-40 weight % are stated, wherein, the matrix is selected from oxygen
Change at least one of aluminium, silica, amorphous silica-alumina, zirconium oxide, titanium oxide, boron oxide and alkaline earth oxide；With institute
On the basis of the total weight for stating catalyst, the content of the active component coating is 15-40 weight %.
12. catalyst according to claim 1, wherein, the ordered structure carrier is selected from parallel with both ends open
The monolithic substrate of pore passage structure.
13. catalyst according to claim 12, wherein, the hole density in the section of the ordered structure carrier is 6-140
Hole/square centimeter, the sectional area in each hole is 0.4-10 square millimeters, percent opening 50-80%.
14. according to the catalyst described in any one in claim 1,12 and 13, wherein, the ordered structure carrier is selected from violet
At least one of green stone honeycomb substrate, mullite honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrate.
15. a kind of method for the catalyst for preparing naphtha catalytic cracking production propylene described in claim 1, this method include：
(1) the first molecular sieve, the second molecular sieve, third molecular sieve are respectively mixed and ground with aqueous solvent, obtain first point
Sub- screening the pulp liquid, the second molecular sieve pulp and third molecular sieve pulp；
(2) the first molecular sieve pulp, the second molecular sieve pulp and third molecular sieve pulp respectively with substrate source are mixed, obtains
One active component coating slurries, the second active component coating slurries and third active component coating slurries；
(3) ordered structure carrier, dry roasting, then with the first activearm are coated with the third active component coating slurries
Divide coating slurry coating that the ordered structure carrier of third active component coating, dry roasting is distributed with；Then with the second activity
Component coating slurry coats the ordered structure carrier that third active component coating and the first active component coating is distributed with, after dry
Roasting.
16. the method according to claim 11, wherein, in step (1), first molecular sieve pulp, the second molecular sieve
The sieve particle diameter d of slurries and third molecular sieve pulp90Respectively 1-10 microns, first molecular sieve pulp, second
The solid content of molecular sieve pulp and third molecular sieve pulp is respectively 15-70 weight %, and the aqueous solvent is deionized water.
17. the method according to claim 11, wherein, in step (2), the first active component coating slurries, second
Respectively also contain dispersant, first active component coating in active component coating slurries and third active component coating slurries
The weight ratio of dispersant and first molecular sieve is 0.0001-0.004 in slurries：1, the second active component coating slurries
The weight ratio of dispersant and second molecular sieve is 0.0001-0.0005：1, the third active component coating slurries dispersion
The weight ratio of agent and the third molecular sieve is 0.0002-0.0004：1.
18. the catalyst as made from the method described in any one in claim 15-17.
19. 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 1-14 and
Catalyst in 18 described in any one.
20. according to the method for claim 19, 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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