CN105562078B - Naphtha catalytic cracking produces the method that catalyst of propylene and preparation method thereof and naphtha catalytic cracking produce propylene - Google Patents
Naphtha catalytic cracking produces the method that catalyst of propylene and preparation method thereof and naphtha catalytic cracking produce propylene Download PDFInfo
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Abstract
The present invention provides a kind of catalyst and preparation method thereof of naphtha catalytic cracking production propylene, 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 and the second molecular sieve；First molecular sieve is the molecular sieve with the one-dimensional ellipse cellular structure of ten-ring, and second molecular sieve is the molecular sieve with twelve-ring cellular structure.The present invention also provides a kind of methods that naphtha catalytic cracking produces propylene.Using catalyst provided by the invention, the yield of propylene can be improved, and obtain propylene/ethylene 2 or more.
Description
Technical field
Catalyst of propylene and preparation method thereof is produced the present invention relates to naphtha catalytic cracking and naphtha catalytic cracking produces
A kind of method of propylene, and in particular, to naphtha catalytic cracking produces the catalyst of propylene, a kind of to prepare naphtha catalytic cracking
A kind of method that the method and its catalyst obtained and naphtha catalytic cracking for producing the catalyst of propylene produce propylene.
Background technique
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 mainly passes through steam heat producing ethylene by cracking and propylene by raw material of naphtha, wherein by
The limitation of heat scission reaction mechanism, general ethylene are major product, and propylene is byproduct, and propylene/ethylene ratio is maximum limit about
0.65, it is higher than this ratio, total olefin will decline.This process needs to consume a large amount of high-quality feed naphtha, is one
The process of high energy consumption.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 lower.And catalytic pyrolysis
Reaction mechanism advantageously forms propylene molecules, therefore naphtha production propene yield may be implemented and increase.
CN101491772A discloses a kind of catalyst for naphtha catalytic cracking, include by weight percentage 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 zeolite
At least one of sieve or the coexisting molecular sieve of ZSM-5 and Y zeolite；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 ethylene and propylene that the catalyst can obtain is also
It is lower.
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 screen containing 60-90%, the heteropoly acid of 0.5-3%.The catalyst is actually used in
When 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
The catalyst of catalytic pyrolysis production propylene.
Summary of the invention
When producing propylene the purpose of the invention is to overcome the prior art to carry out naphtha catalytic cracking, propylene yield is small
Problem provides the side that naphtha catalytic cracking produces catalyst of propylene and preparation method thereof and naphtha catalytic cracking produces propylene
Method.
To achieve the goals above, 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
Sieve contains the first molecular sieve and the second molecular sieve；First molecular sieve is point with the one-dimensional ellipse cellular structure of ten-ring
Son sieve, second molecular sieve are the molecular sieve with twelve-ring cellular structure.
The present invention also provides a kind of method for preparing naphtha catalytic cracking and producing the catalyst of propylene, this method includes：
(1) molecular sieve and aqueous solvent are mixed and is ground, obtain molecular sieve pulp；
(2) molecular sieve pulp is mixed with substrate source, 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 and the second molecular sieve；First molecular sieve is with ten-ring
The molecular sieve of one-dimensional ellipse cellular structure, second molecular sieve are the molecular sieve with twelve-ring cellular structure.
The present invention also provides catalyst made from method provided by the present invention.
The present invention also provides a kind of method that naphtha catalytic cracking produces 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 obtain propylene/ethylene 2 or more.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.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, is referred to using term ordered structure catalyst including ordered structure carrier 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 the catalyst that a kind of naphtha catalytic cracking produces propylene, which includes：Ordered structure carries
Body and the active component coating for being distributed in ordered structure inner surface of the carrier and/or outer surface；Total weight with the catalyst is
Benchmark, the content of the active component coating are 10-50 weight %；On the basis of the total weight of the active component coating, institute
State the matrix of molecular sieve and 5-50 weight % that active component coating contains 50-95 weight %；The molecular sieve contains first point
Son sieve and the second molecular sieve；First molecular sieve is the molecular sieve with the one-dimensional ellipse cellular structure of ten-ring, described the
Two molecular sieves are the molecular sieve with twelve-ring cellular structure.
In the present invention, use the molecular sieve for containing the first molecular sieve and the second molecular sieve as lytic activity component, it can
Obtain the yield that high naphtha catalytic cracking produces propylene.
According to a preferred embodiment of the present invention, the active component coating includes inside and outside two layers, wherein internal layer
Containing first molecular sieve, outer layer contains second molecular sieve.Wherein internal layer refers to connecing with ordered structure carrier peripheral wall
The layer of touching；Outer layer refers to the layer arranged extruded on internal layer, close to pipeline center.
, according to the invention it is preferred to internal layer active component coating total weight, the first molecular sieve containing 50-95 weight %
With the matrix of 5-50 weight %；With outer layer active component coating total weight, the second molecular sieve and 5- containing 50-95 weight %
The matrix of 50 weight %.
In the present invention, for internal layer coating using the first molecular sieve as catalytic cracking activity component, outer coating uses second
As catalytic cracking activity component, and respectively active component is made in first molecular sieve and the second molecular sieve and matrix by molecular sieve
Coating is distributed on ordered structure carrier, forms ordered structure catalyst, can be obtained higher naphtha catalytic cracking and be produced third
The yield of alkene.
According to the present invention, first molecular sieve is the molecular sieve with the one-dimensional ellipse cellular structure of ten-ring, preferably
Channel openings diameter is at 0.45-0.56 nanometers.
, according to the invention it is preferred to first molecular sieve be TON structure molecular sieve and/or MTT structure molecular sieve,
Middle structure type TON, MTT refers 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 TON structure, including Theta-1 zeolite, ISI-1 zeolite, KZ-2 zeolite, NU-10 boiling
Stone, ZSM-22 zeolite and SSZ-32 zeolite etc., the molecular sieve of MTT structure include ZSM-23 zeolite, EU-13 zeolite, ISI-4 zeolite
With KZ-1 zeolite etc..
For the present invention, preferably described first molecular sieve is Theta-1 zeolite, ISI-1 zeolite, KZ-2 zeolite, NU-10 boiling
At least one in stone, ZSM-22 zeolite, SSZ-32 zeolite, ZSM-23 zeolite, EU-13 zeolite, ISI-4 zeolite and KZ-1 zeolite
Kind.
, according to the invention it is preferred to which first molecular sieve is the mixing of the molecular sieve of TON structure and the molecular sieve of MTT structure
Object.It is further preferred that the weight ratio of the molecular sieve of the TON structure and the molecular sieve of MTT structure is 0.1-10:1, more preferably 1-5:
1。
According to the preferred embodiment of the present invention, the molecular sieve of the TON structure, preferably includes Theta-1 zeolite, ISI-
One of 1 zeolite, KZ-2 zeolite, NU-10 zeolite, ZSM-22 zeolite and SSZ-32 zeolite are a variety of.
According to the preferred embodiment of the present invention, the molecular sieve of the MTT structure, preferably includes ZSM-23 zeolite, EU-13
One of zeolite, ISI-4 zeolite and KZ-1 zeolite are a variety of.
A preferred embodiment of the invention, the molecular sieve of the TON structure are that ZSM-22 zeolite and NU-10 boil
The mixture of stone, the weight ratio of the two are 2-5:1；The molecular sieve of the MTT structure is the mixed of ISI-4 zeolite and ZSM-23 zeolite
Object is closed, the weight ratio of the two is 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 diameter of second molecular sieve is 0.65-0.7 nanometers.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 the molecular sieve of MOR, OFF and SAO structure.It is particularly preferred that second molecular sieve be 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 can be 0.1-100 in second molecular sieve：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 1-15：1,
Preferably 1.5-7：1.
In accordance with the present invention it is preferred that the active component coating contains on the basis of the total weight of the active component coating
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 monolith, and inside forms hollow cellular 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 honeycomb aperture
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 be the hole 6-140/square li
Rice, the hole preferably 20-100/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
The wing that position has vertical edges inside, the length is the 1/5-2/5 of square side length), equilateral triangle, regular hexagon, circle and wave
One of 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 to require, 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 is mixed with substrate source, 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 and the second molecular sieve；First molecular sieve is with ten-ring
The molecular sieve of one-dimensional ellipse cellular structure, second molecular sieve are the molecular sieve with twelve-ring cellular structure.
A kind of preferred embodiment according to the present invention, method of the invention prepare catalyst as follows：(1)
First molecular sieve and the second molecular sieve are respectively mixed and ground with aqueous solvent, the first molecular sieve pulp and the second molecule are obtained
Screening the pulp liquid；
(2) first molecular sieve pulp, the second molecular sieve pulp are respectively mixed with substrate source, forms the first active group
Divide coating slurry and the second active component coating slurries；
(3) ordered structure carrier is coated with the first active component coating slurries, dry roasting is then living with second
Property the coating of component coating slurry the ordered structure carrier of the first active component coating, dry roasting is distributed with.
In the case of, according to the invention it is preferred to, active group that the additional amount of the substrate source and the molecular sieve makes
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 substrate source is used to provide the matrix in the active component being prepared, 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 contain aluminium oxide and silica, but the amount of the silica and aluminium oxide contained 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 50-65 weight %, and the aqueous solvent is water example
Such as deionized water.
According to a preferred embodiment of the present invention, the first molecular sieve pulp described in step (1) and the second molecule
The sieve particle diameter d of screening the pulp liquid90Respectively 1-10 microns, such as 5-10 microns, first molecular sieve pulp and second
The solid content of molecular sieve pulp is respectively 15-70 weight %, such as 50-65 weight %, the aqueous solvent be water for example go from
Sub- 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 10-40 weight %, total content of the substrate source in terms of matrix
For 0.3-18 weight %, preferably 4-15 weight %.
According to a preferred embodiment of the present invention, with the first active component coating slurries and the second active group
Divide on the basis of the respective total weight of coating slurry, the content of first molecular sieve (or second molecular sieve) is respectively 3-60 weight
%, preferably 10-40 weight % are measured, total content of the substrate source in terms of matrix is 0.3-18 weight %, preferably 4-15 weight
Measure %.
According to a preferred embodiment of the present invention, the first active component coating slurries and the second active component are formed
The matrix source category and dosage of coating slurry can be identical or different, can specifically be selected according to actual needs.
According to the present invention, active component coating slurries described in step (2) can also contain dispersing agent, the dispersing agent with
The weight ratio of the molecular sieve is 0.2 or less and is greater than 0；Preferably 0.0005-0.015：1.
A preferred embodiment of the invention, described in the first active component coating slurries described in step (2) point
The weight ratio of powder and first molecular sieve is 0.0005-0.015：1, disperse described in the second active component coating slurries
The weight ratio of agent and second molecular sieve is 0.0006-0.002：1.
According to the present invention, dispersing agent described in step (2) in containing polyhydroxy, polyvinyl and polycarboxylic acids base extremely
One of compound, such as polyethylene glycol, glycerine, polyvinyl alcohol or polyacrylic acid of a kind of few group are a variety of, preferably
For polyethylene glycol and/or polyacrylic acid.
According to the present invention, step (3) can by various coating 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 concrete operations of coating are referred to the progress of method described in CN1199733C.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, when 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 is roasted.
The method and condition of the drying is known to those skilled in the art, for example, dry method can be and dry, dries, rouse
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 of roasting described in step (3) may be known to one of skill in the art, general next
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, the preferably described silica source
It is greater than the natural crystal of 45 weight % for silica or silica content.Preferably, the silica source can for laminated clay column,
At least one of diatomite, expanded perlite, silicalite, silica solution, 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 of aluminium, Aluminum sol and boehmite or a variety of；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 weight
Measure %；On the basis of the total weight of the active component coating, the active component coating contains the molecular sieve of 50-95 weight %
With the matrix of 5-50 weight %；The molecular sieve contains the first molecular sieve and the second molecular sieve；First molecular sieve be with
The molecular sieve of the one-dimensional ellipse cellular structure of ten-ring, second molecular sieve are the molecule with twelve-ring cellular structure
Sieve.
The present invention also provides a kind of method that naphtha catalytic cracking produces 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/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 model
Device measurement.Yield and selectivity are calculated by the following formula to obtain：
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 to illustrate that the preparation method of catalyst provided by the invention and naphtha catalytic cracking to produce propylene
Method.
Prepare catalyst.By 56.2 grams of ZSM-22 molecular sieves (Nanjing Ji Cang nanosecond science and technology Co., Ltd, Si/Al molar ratio
=30：1) it is mixed with 56.2 grams of deionized waters, wet ball grinding is at molecular sieve pulp, sieve particle diameter d90=10 microns, Gu
Content is 50 weight %.28.4 grams of Aluminum sols (salic 22 weight %, middle Effect of Catalysis In Petrochemistry agent Shandong point public affairs are added in slurries
Department produces), it stirs 10 minutes, 1.5 grams of polyglycol solution (polyglycol solution weight percent is 2 weight %) is added, stirs
It mixes and obtains within 20 minutes the first active component coating slurries 1.
By the first active component coating slurries 1 coat cordierite honeycomb carrier (carrier hole density be 100 holes/square centimeter,
The sectional area in each hole is 7 square millimeters, and the shape of percent opening 80%, hole is square), dry 5 hours simultaneously at 120 DEG C
It is roasted 5 hours at 500 DEG C, obtains catalyst precarsor 1, wherein active component coating content is 15 weight %.
By 30 grams of Beta molecular sieves (self-control, molar ratio=50 Si/Al：1) mixed with 30 grams of deionized waters, wet ball grinding at
Molecular sieve pulp, d90=10 microns of sieve particle diameter, solid content is 50 weight %.It is molten that 15.0 grams of aluminium are added in slurries
Glue (salic 22 weight %, middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery produce), stirs 10 minutes, polyglycol solution is added
1.0 grams (polyglycol solution weight percent is 2 weight %), stirring obtains catalyst coat for 20 minutes and prepares the second active group
Divide coating slurry 2.
Second active component coating slurries 2 are coated and roast 5 at dry 5 hours and 500 DEG C at 1,120 DEG C of catalyst precarsor
Hour, wherein outer layer active component coating content is 9 weight %.With active component coating total weight, molecular sieve content 90
Weight %, matrix (aluminium oxide) content are 10 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, the 56 weight % containing alkane, 32 weight containing cycloalkane
Amount %, the 11 weight % containing aromatic hydrocarbons, 0.5 μ g/g of basic nitrogen) and water through 250 DEG C preheat after inject above-mentioned monolithic reactors.Its
In, the weight (hourly) space velocity (WHSV) (total weight relative to 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 to illustrate that the preparation method of catalyst provided by the invention and naphtha catalytic cracking to produce propylene
Method.
(1) catalyst is prepared.
By 32 grams of ZSM-23 molecular screen powder (Shanghai Zhuo Yue Chemical Co., Ltd., molar ratio=50 Si/Al：1)) with 20 grams
Deionized water mixing, wet ball grinding is at slurries, d90=8 microns of sieve particle diameter in slurries；150 grams are added in slurries
Peptization boehmite (salic 18 weight %, pH value 2.8, middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery product), stirring 15
Minute；3.2 grams of polyacrylic acid solution (polyacrylic acid solution weight percent is 1 weight %) is added, polyacrylic acid solution is added
Amount is 10 weight % of molecular sieve, stirs 30 minutes, obtains the first active component coating slurries 1.
By the first active component coating slurries 1, coat cordierite honeycomb carrier (carrier hole density is 80 holes/square centimeter,
The sectional area in each hole is 5 square millimeters, percent opening 60%, and the shape in hole is circle), dry 5 hours and 500 at 120 DEG C
It is roasted 5 hours at DEG C, obtains catalyst precarsor 1, wherein active component coating content is 10 weight %.
By 32 grams of mordenite molecular sieves (Shanghai Shen Tan environmental friendly material Co., Ltd, molar ratio=80 Si/Al：1) with
30 grams of deionized water mixing, wet ball grinding is at molecular sieve pulp, and d90=10 microns of sieve particle diameter, solid content is 50 weights
Measure %.122 grams of Aluminum sols (salic 22 weight %, middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery produce) is added in slurries, stirs
It mixes 10 minutes, is added 1.0 grams of polyglycol solution (polyglycol solution weight percent is 2 weight %), stirring 20 minutes
The second active component coating slurries 2 are prepared to catalyst coat.
Second active component coating slurries 2 are coated and roast 5 at dry 5 hours and 500 DEG C at 1,120 DEG C of catalyst precarsor
Hour, wherein outer layer active component coating content is 10 weight %.With active component coating total weight, molecular sieve content is
54 weight %, matrix (silica) content are 46 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, the 56 weight % containing alkane, 32 weight containing cycloalkane
Amount %, the 11 weight % containing aromatic hydrocarbons, 0.4 μ g/g of basic nitrogen) and water through 250 DEG C preheat after inject above-mentioned monolithic reactors.Its
The weight (hourly) space velocity (WHSV) (total weight relative to 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 to illustrate that the preparation method of catalyst provided by the invention and naphtha catalytic cracking to produce propylene
Method.
(1) catalyst is prepared.By 70 grams of NU-10 molecular sieves (self-control, molar ratio=80 Si/Al：1) mixed with 60 grams of distilled water
It closes, wet ball grinding is at slurries, d90=5 microns of sieve particle diameter in slurries；143 grams of acidic silicasols are added in slurries
(21 weight % of silicon oxide-containing, middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery product) stirs 60 minutes；Polyethylene glycol and polypropylene is added
12.6 grams of sour mixed solution (polyethylene glycol and polyacrylic acid weight percent are divided into 3 weight % and 5 weight %) stirs 30 minutes
Obtain the first active component coating slurries 1.
By the first active component coating slurries 1 coat cordierite honeycomb carrier (carrier hole density be 20 holes/square centimeter,
The sectional area in each hole is 2 square millimeters, percent opening 75%, and the shape in hole is circle), dry 5 hours and 500 at 120 DEG C
It is roasted 5 hours at DEG C, obtains catalyst precarsor 1, wherein active component coating content is 20 weight %.
By 10 grams of (molar ratio=40 Si/Al SSZ-13：1) it is mixed with 10 grams of deionized waters, wet ball grinding is at molecule screening the pulp
Liquid, d90=10 microns of sieve particle diameter, solid content is 50 weight %.20 grams of silica solution (silicon oxide-containings are added in slurries
21 weight %, middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery produce), it stirs 10 minutes, 1.0 grams of polyglycol solution (poly- second two is added
Alcoholic solution weight percent is 2 weight %), stirring obtains catalyst coat for 20 minutes and prepares the second active component coating slurries 2.
Second active component coating slurries 2 are coated and roast 5 at dry 5 hours and 500 DEG C at 1,120 DEG C of catalyst precarsor
Hour, wherein outer layer active component coating content is 10 weight %.
With active component coating total weight：Molecular sieve content is 70 weight %, and matrix (silica) content is 30 weights
Measure %.
(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, the 56 weight % containing alkane, 32 weight containing cycloalkane
Amount %, the 11 weight % containing aromatic hydrocarbons, 0.6 μ g/g of basic nitrogen) and water through 250 DEG C preheat after inject above-mentioned monolithic reactors.Its
The weight (hourly) space velocity (WHSV) (total weight relative to 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.
Comparative example 1
According to the method for embodiment 1, unlike, ZSM-22 zeolite is replaced by the Beta zeolite of equivalent, i.e., molecular sieve is complete
Portion is the second molecular sieve.
Comparative example 2
According to the method for embodiment 1, unlike, Beta zeolite is replaced by the ZSM-22 zeolite of equivalent, i.e., molecular sieve is complete
Portion is the first molecular sieve.
Comparative example 3
It carries out according to the method for embodiment 1, unlike, the catalyst used is prepared as follows：
By 56.2 grams of ZSM-5 molecular sieves (Nankai University's production, molar ratio=30 Si/Al：1) mixed with 56.2 grams of deionized waters
It closing, wet ball grinding is at molecular sieve pulp, and d90=10 micron of sieve particle diameter, solid content is 50 weight %.In slurries
28.4 grams of Aluminum sols (salic 22 weight %, middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery produce) is added, stirring obtains for 20 minutes
Mix slurry is through extruded moulding.
In catalyst：ZSM-5 molecular sieve content is 90 weight %, and matrix (aluminium oxide) content is 10 weight %.
Embodiment 4
According to the method cracking naphtha of embodiment 3, the difference is that, the first molecular sieve is by ZSM-22 zeolite in catalyst
(sial atomic molar ratio is by 30) and ISI-4 zeolite (sial atomic molar ratio is by 30) 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, the first molecular sieve is by NU-10 zeolite (silicon in catalyst
80) aluminium atom molar ratio with ZSM-23 zeolite (sial atomic molar ratio is by 50) by replacing, 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, the first molecular sieve is by SSZ-32 zeolite in catalyst
(sial atomic molar ratio is by 30) and KZ-1 zeolite (sial atomic molar ratio is by 50) replace, and the weight ratio of the two is 5:1.
Embodiment 7
According to the method cracking naphtha of embodiment 4, unlike, in catalyst the first molecular sieve ZSM-22 zeolite by
ZSM-22 zeolite (sial atomic molar ratio is 30) and NU-10 zeolite (sial atomic molar ratio is 30), the weight ratio of the two is
3:1；ISI-4 zeolite is by ISI-4 zeolite (sial atomic molar ratio is 30) and ZSM-23 zeolite (sial atomic molar ratio is 30)
Mixture replace, 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 and the second active component are applied
Coating ordered structure carrier is carried out after layer slurries mixing, is then dried and roasts, dry and roasting temperature and embodiment 3
Identical, dry and roasting total time is identical after coating with embodiment 3 total time of dry total time and roasting, remaining condition
It is all the 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, dry and roasting temperature is same as Example 3, remaining condition is all the same.
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 contain double-layer active component coating；Wherein internal layer molecular sieve has the one-dimensional ellipse duct knot of ten-ring
Structure, is one kind of TON or MTT structure, and outer layer has the molecular sieve in twelve-ring duct.Third is produced carrying out naphtha catalytic cracking
In alkene, high ethylene and propene yield can be obtained, and wherein propylene/ethylene ratio is greater than 2, and producing more propylene may be implemented.
Claims (19)
1. a kind of naphtha catalytic cracking produces the catalyst of propylene, which includes：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 active group
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 contains the first molecular sieve and the second molecular sieve；
First molecular sieve is the molecular sieve with the one-dimensional ellipse cellular structure of ten-ring, and second molecular sieve is with 12
The molecular sieve of membered ring channel structure, the active component coating include inside and outside two layers, wherein internal layer contains first molecule
Sieve, outer layer contain second molecular sieve；First molecular sieve is the molecular sieve of TON structure and/or the molecule of MTT structure
Sieve, second molecular sieve be selected from AET, AFR, AFS, AFI, BEA, BOG, CFI, CON, GME, IFR, ISV, LTL, MEI,
At least one of the molecular sieve of MOR, OFF and SAO structure；The weight ratio of first molecular sieve and second molecular sieve is
1-15：1.
2. catalyst according to claim 1, wherein with internal layer active component coating total weight, contain 50-95 weight
Measure the first 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.
3. catalyst according to claim 1 or 2, wherein the molecular sieve of the TON structure include Theta-1 zeolite,
One of ISI-1 zeolite, KZ-2 zeolite, NU-10 zeolite, ZSM-22 zeolite and SSZ-32 zeolite are a variety of；The MTT structure
Molecular sieve include one of ZSM-23 zeolite, EU-13 zeolite, ISI-4 zeolite and KZ-1 zeolite or a variety of.
4. catalyst according to claim 1 or 2, wherein first molecular sieve is the molecular sieve and MTT of TON structure
The mixture of the molecular sieve of structure.
5. catalyst according to claim 4, wherein the weight of the molecular sieve of the molecular sieve and MTT structure of the TON structure
Amount is than being 0.1-10:1.
6. catalyst according to claim 4, wherein the weight of the molecular sieve of the molecular sieve and MTT structure of the TON structure
Amount is than being 1-5:1.
7. catalyst according to claim 3, wherein the molecular sieve of the TON structure is that ZSM-22 zeolite and NU-10 boil
The mixture of stone, the weight ratio of the two are 2-5:1；The molecular sieve of the MTT structure is the mixed of ISI-4 zeolite and ZSM-23 zeolite
Object is closed, the weight ratio of the two is 2-5:1.
8. catalyst according to claim 1 or 2, wherein the channel openings diameter of second molecular sieve is 0.6-
0.75 nanometer.
9. catalyst according to claim 1 or 2, wherein described on the basis of the total weight of the active component coating
Active component coating contains the molecular sieve of 54-90 weight % and the matrix of 10-46 weight %；Total weight with the catalyst is
Benchmark, the content of the active component coating are 15-30 weight %.
10. catalyst according to claim 1 or 2, wherein the ordered structure carrier is selected from flat with both ends open
The monolithic substrate of row cellular structure.
11. catalyst according to claim 1 or 2, wherein the hole density in the section of the ordered structure carrier is 6-
140 holes/square centimeter, the sectional area in each hole are 0.4-10 square millimeters, percent opening 50-80%.
12. catalyst according to claim 1 or 2, wherein the ordered structure carrier be selected from cordierite honeycomb carrier,
At least one of mullite honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrate.
13. catalyst according to claim 1 or 2, wherein the matrix is selected from aluminium oxide, silica, amorphous silicon
At least one of aluminium, zirconium oxide, titanium oxide, boron oxide and alkaline earth oxide.
14. a kind of method for preparing naphtha catalytic cracking described in claim 1 and producing the catalyst of propylene, this method include：
(1) the first molecular sieve and the second molecular sieve are respectively mixed and are ground with aqueous solvent, obtain the first molecular sieve pulp and
Second molecular sieve pulp；
(2) first molecular sieve pulp, the second molecular sieve pulp are respectively mixed with substrate source, forms the first active component and applies
Layer slurries and the second active component coating slurries；
(3) ordered structure carrier, dry roasting, then with the second active group are coated with the first active component coating slurries
The ordered structure carrier for dividing coating slurry coating that the first active component coating is distributed with, dry roasting.
15. according to the method for claim 14, wherein in step (1), first molecular sieve pulp and the second molecular sieve
The sieve particle diameter d of slurries90Respectively 1-10 microns, first molecular sieve pulp and consolidating for the second molecular sieve pulp contain
Amount is respectively 15-70 weight %, and the aqueous solvent is deionized water.
16. according to the method for claim 14, wherein in step (2), the first active component coating slurries and the second activity
Respectively also contain dispersing agent, dispersing agent described in the first active component coating slurries and described first in component coating slurry
The weight ratio of molecular sieve is 0.0005-0.015：1, dispersing agent described in the second active component coating slurries and described second
The weight ratio of molecular sieve is 0.0006-0.002：1.
17. catalyst made from the method as described in any one of claim 14-16.
18. a kind of method that naphtha catalytic cracking produces propylene, this method include：Under naphtha catalytic cracking reaction condition,
Naphtha and water are contacted with catalyst, obtain propylene product, which is characterized in that the catalyst include claim 1-13 and
Catalyst described in any one of 17.
19. according to the method for claim 18, 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, and 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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| WO2005035118A1 (en) * | 2003-09-25 | 2005-04-21 | Exxonmobil Chemical Patents Inc. | Multi component catalyst and its use in catalytic cracking |
| 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 |
| ES2343937A1 (en) * | 2009-01-29 | 2010-08-12 | Uop Llc | Fcc catalyst for production of lightweight olefins (Machine-translation by Google Translate, not legally binding) |
| US7973209B1 (en) * | 2006-09-28 | 2011-07-05 | Uop Llc | Fractionation recovery processing of light olefins free of carbon dioxide |
| CN102451731A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation and application of honeycomb carrier catalyst coating slurry |
| CN102451742A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of honeycomb carrier catalyst comprising molecular sieve composition coating |
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|---|---|---|---|---|
| WO2005035118A1 (en) * | 2003-09-25 | 2005-04-21 | Exxonmobil Chemical Patents Inc. | Multi component catalyst and its use in catalytic cracking |
| 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 |
| US7973209B1 (en) * | 2006-09-28 | 2011-07-05 | Uop Llc | Fractionation recovery processing of light olefins free of carbon dioxide |
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| CN102451731A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation and application of honeycomb carrier catalyst coating slurry |
| CN102451742A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of honeycomb carrier catalyst comprising molecular sieve composition coating |
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