CN105562072A - Catalyst for producing propylene by catalytic cracking of naphtha and preparation method thereof as well as method for producing propylene by catalytic cracking of naphtha - Google Patents
Catalyst for producing propylene by catalytic cracking of naphtha and preparation method thereof as well as method for producing propylene by catalytic cracking of naphtha Download PDFInfo
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Abstract
The invention provides a catalyst for producing propylene by the catalytic cracking of naphtha and a preparation method thereof. The catalyst comprises a regular structure carrier and an active ingredient coating distributed on the inner surface and/or the outer surface of the regular structure carrier; a molecular sieve adopts a ten-membered cyclic one-dimensional elliptic porous structure. The invention further provides a method for producing propylene by the catalytic cracking of naphtha. With adoption of the catalyst provided by the invention, the yield of propylene can be increased, and the ratio of propylene to ethylene is 1 or above.
Description
Technical field
The present invention relates to naphtha catalytic cracking and produce the Catalysts and its preparation method of propylene and the method for naphtha catalytic cracking product propylene, particularly, relate to the catalyst that a kind of naphtha catalytic cracking produces propylene, prepare naphtha catalytic cracking and produce the method for the catalyst of propylene and an obtained catalyst thereof, and a kind of naphtha catalytic cracking produces the method for propylene.
Background technology
Propylene is one of most widely used basic organic chemical industry raw material, mainly for the production of polypropylene, isopropylbenzene, acrylonitrile, acrylic acid etc.Current propylene is mainly derived from the ethylene cracker of petrochemical plant and the catalytic cracking unit of oil plant.Along with global propylene demand increases fast, the output of traditional processing technology is difficult to satisfy the demands, and the technology therefore developing propylene enhancing has become an important development direction in petrochemical iy produced technology.
Conventional ethylene cracking is mainly that raw material passes through steam heat producing ethylene by cracking and propylene with naphtha, and wherein limit by heat scission reaction mechanism, general ethene is major product, propylene is byproduct, propylene/ethylene ratio is for maximum limit is about 0.65, and higher than this ratio, total olefin will decline.The high-quality feed naphtha that this process need consumption is a large amount of is the process of a high energy consumption.The propylene steam heat cracking technique of current 66-70% is produced.
Catalytic pyrolysis about 50-200 DEG C lower than the reaction temperature of steam heat cracking, energy consumption is lower.And the reaction mechanism of catalytic pyrolysis is conducive to forming propylene molecules, therefore can realizes naphtha and produce propene yield increase.
CN101491772A discloses a kind of catalyst for naphtha catalytic cracking, comprises following active component by weight percentage: a) 80-99.5% is selected from least one in the coexisting molecular sieve of the coexisting molecular sieve of ZSM-5 and modenite, the coexisting molecular sieve of ZSM-5 and β zeolite or ZSM-5 and Y zeolite; With carry b thereon) surplus be selected from least one element in periodic table of elements VA race element or its oxide.But the diene yield of the ethene that this catalyst can obtain and propylene is also lower.
CN102861604A discloses a kind of producing olefin hydrocarbon by catalytic pyrolysis of naphtha catalyst, wherein, by the weight content of final catalyst, and the EU-1/ZSM-5 composite molecular screen containing 60-90%, the heteropoly acid of 0.5-3%.When this catalyst is actually used in naphtha catalytic cracking, although can ethene and proprene diene yield high, propylene/ethylene is lower than also, and the propone output of acquisition is little.
As can be seen here, carry out naphtha catalytic cracking and will realize more large-tonnage propylene, also need the new catalyst producing propylene for naphtha catalytic cracking.
Summary of the invention
The object of the invention is in order to overcome prior art carry out naphtha catalytic cracking produce propylene time, the problem that propone output is little, provide naphtha catalytic cracking to produce method that the Catalysts and its preparation method of propylene and naphtha catalytic cracking produce propylene.
To achieve these goals, the invention provides the catalyst that a kind of naphtha catalytic cracking produces propylene, this catalyst comprises ordered structure carrier and is distributed in the active component coating of ordered structure carrier inner surface and/or outer surface; With the gross weight of described catalyst for benchmark, the content of described active component coating is 10-50 % by weight; With the gross weight of described active component coating for benchmark, described active component coating contains the molecular sieve of 50-95 % by weight and the matrix of 5-50 % by weight; Described molecular sieve is the molecular sieve with ten-ring one dimension ellipse pore passage structure.
Present invention also offers a kind of method preparing the catalyst of naphtha catalytic cracking product propylene, the method comprises: molecular sieve and aqueous solvent mix and grind by (1), obtain molecular sieve pulp, described molecular sieve is the molecular sieve with ten-ring one dimension ellipse pore passage structure; (2) described molecular sieve pulp is mixed with substrate source, form active component coating slurries; (3) with the also dry and roasting of described active component coating slurries coating ordered structure carrier.
Present invention also offers the catalyst obtained by method provided by the invention.
Present invention also offers a kind of naphtha catalytic cracking and produce the method for propylene, the method comprises: under naphtha catalytic cracking reaction condition, and by naphtha and water and catalyst exposure, obtain propylene product, wherein, described catalyst is catalyst provided by the invention.
Adopt catalyst provided by the invention, the yield of propylene can be improved, and obtain propylene/ethylene more than 1.Such as, in embodiment 1, adopt ordered structure carrier and containing have ten-ring one dimension ellipse pore passage structure the catalyst of active component coating, in the product that naphtha catalytic cracking obtains, C
2 =-C
4 =selective be 90.55%, C
2 =+ C
3 =yield be 68.13%, C
3 =/ C
2 =be 1.64, can producing more propylene be realized.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
In the present invention, term ordered structure catalyst is used to refer to the catalyst of the active component coating comprising ordered structure carrier and be distributed in carrier inner surface and/or outer surface; Ordered structure carrier be there is ordered structure carrier as honeycomb substrate; Monolithic reactors is loaded the fixed bed reactors of ordered structure catalyst as beds.
The invention provides the catalyst that a kind of naphtha catalytic cracking produces propylene, this catalyst comprises ordered structure carrier and is distributed in the active component coating of ordered structure carrier inner surface and/or outer surface; With the gross weight of described catalyst for benchmark, the content of described active component coating is 10-50 % by weight; With the gross weight of described active component coating for benchmark, described active component coating contains the molecular sieve of 50-95 % by weight and the matrix of 5-50 % by weight; Described molecular sieve is the molecular sieve with ten-ring one dimension ellipse pore passage structure.
The present invention is adopted as the molecular sieve with ten-ring one dimension ellipse pore passage structure, be preferably the one of TON structure or MTT structure, as catalytic cracking activity component, and molecular sieve and matrix being made active component coating is distributed on ordered structure carrier, form ordered structure catalyst, the yield that higher naphtha catalytic cracking produces propylene can be obtained.
According to the present invention, described molecular sieve is the molecular sieve with ten-ring one dimension ellipse pore passage structure, and preferred duct opening diameter is in 0.45-0.56 nanometer.
According to the present invention, preferred described molecular sieve is the molecular sieve of TON structure and/or the molecular sieve of MTT structure, wherein structure type TON, MTT refer to the molecular sieve structure that International Zeolite Association meeting (IZA) is named, for describing the Space expanding in duct in molecular sieve.The molecular sieve of described TON structure, comprises Theta-1 zeolite, ISI-1 zeolite, KZ-2 zeolite, NU-10 zeolite, ZSM-22 zeolite and SSZ-32 zeolite etc., and the molecular sieve of MTT structure comprises ZSM-23 zeolite, EU-13 zeolite, ISI-4 zeolite and KZ-1 zeolite etc.
For the present invention, preferred described molecular sieve is at least one in Theta-1 zeolite, ISI-1 zeolite, KZ-2 zeolite, NU-10 zeolite, ZSM-22 zeolite, SSZ-32 zeolite, ZSM-23 zeolite, EU-13 zeolite, ISI-4 zeolite and KZ-1 zeolite.
According to the present invention, preferred described molecular sieve is the mixture of the molecular sieve of TON structure and the molecular sieve of MTT structure.More preferably, the weight ratio of the molecular sieve of described TON structure and the molecular sieve of MTT structure is 0.1-10:1, is more preferably 1-5:1.
According to the preferred embodiment of the present invention, the molecular sieve of described TON structure, preferably include in Theta-1 zeolite, ISI-1 zeolite, KZ-2 zeolite, NU-10 zeolite, ZSM-22 zeolite and SSZ-32 zeolite one or more.
According to the preferred embodiment of the present invention, the molecular sieve of described MTT structure, preferably include in ZSM-23 zeolite, EU-13 zeolite, ISI-4 zeolite and KZ-1 zeolite one or more.
A preferred embodiment of the invention, the molecular sieve of described TON structure is the mixture of ZSM-22 zeolite and NU-10 zeolite, and the weight ratio of the two is 2-5:1; The molecular sieve of described MTT structure is the mixture of ISI-4 zeolite and ZSM-23 zeolite, and the weight ratio of the two is 2-5:1.
In the present invention, the sial atomic molar ratio (Si/Al) of described molecular sieve can be 0.1-100:1; Be preferably 30-80:1.
According to the present invention, preferably, with the gross weight of described active component coating for benchmark, described active component coating contains the molecular sieve of 54-90 % by weight and the matrix of 10-46 % by weight.
According to the present invention, preferably, with the gross weight of described catalyst for benchmark, the content of described active component coating is 15-30 % by weight.
According to the present invention, described ordered structure carrier may be used for providing beds in fixed bed reactors.This ordered structure carrier can be the carrier block of monoblock, and inside forms hollow pore passage structure, can distribute catalyst coating on the inwall in duct, and space, duct can be used as the flowing space of fluid.Under preferable case, described ordered structure carrier is selected from the monolithic substrate of the parallel channels structure with both ends open.Described ordered structure carrier can be the regular carrier of honeycomb fashion (abbreviation honeycomb substrate) that cross section has cellular perforate.
According to the present invention, under preferable case, the hole density in the cross section of described ordered structure carrier is 6-140 hole/square centimeter, is preferably 20-100 hole/square centimeter; The sectional area in each hole is 0.4-10 square millimeter, is preferably 2-7 square millimeter; Percent opening is 50-80%.The shape in hole can be square (or wing square, namely in square hole, the centre bit of four edges is equipped with the inside wing of vertical edges, and its length is the 1/5-2/5 of the square length of side), equilateral triangle, regular hexagon, circle and corrugated in one.
According to the present invention, under preferable case, described ordered structure carrier can be selected from least one in cordierite honeycomb carrier, mullite honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrate.
According to the present invention, under preferable case, described matrix can be selected from least one in aluminium oxide, silica, amorphous aluminum silicide, zirconia, titanium oxide, boron oxide and alkaline earth oxide, is preferably aluminium oxide and/or silica.
Catalyst of the present invention can be prepared according to various methods, as long as the catalyst of aforementioned claim of the present invention can be prepared, for the present invention, preferred catalyst of the present invention is prepared as follows: molecular sieve and aqueous solvent mix and grind by (1), obtain molecular sieve pulp, described molecular sieve is the molecular sieve with ten-ring one dimension ellipse pore passage structure; (2) described molecular sieve pulp is mixed with substrate source, form active component coating slurries; (3) with the also dry and roasting of described active component coating slurries coating ordered structure carrier.
According to the present invention, under preferable case, the addition of described substrate source and described molecular sieve makes in the active component coating obtained, and with the gross weight of this active component coating for benchmark, the content of matrix is 5-50 % by weight, and the content of molecular sieve is 50-95 % by weight.
In method provided by the invention, described substrate source for providing the matrix in the active component for preparing, the present invention to this without particular/special requirement.It should be noted that, when described matrix be silica and/or aluminium oxide time, although containing aluminium oxide and silica in described molecular sieve, the silica contained in described molecular sieve and the amount of aluminium oxide still can be regarded as the amount of described molecular sieve, are not counted in silica and aluminium oxide.Namely in the active component obtained by method provided by the invention, the content of each component calculates according to inventory.
According to the present invention, the sieve of molecular sieve pulp Middle molecule described in step (1) particle diameter d90 is 1-10 micron, and be preferably 5-10 micron, the solid content of described molecular sieve pulp is 15-70 % by weight, and described aqueous solvent is deionized water.
According to the present invention, preferably, with the gross weight of the described active component coating slurries obtained in step (2) for benchmark, the content of described molecular sieve is 3-60 % by weight, in the total content of the described substrate source of butt for 0.3-18 % by weight.
According to the present invention, active component coating slurries described in step (2) can also contain dispersant, and the weight ratio of described dispersant and described molecular sieve is less than 0.2 and is greater than 0; Be preferably 0.0005-0.015:1.
According to the present invention, described in step (2), dispersant is selected from the compound containing at least one group in polyhydroxy, polyvinyl and polycarboxylic acids base, such as, in polyethylene glycol, glycerine, polyvinyl alcohol or polyacrylic acid one or more, are preferably polyethylene glycol and/or polyacrylic acid.
According to the present invention, step (3) by various painting method by described active component coating grout distribution to the inner surface and/or outer surface of ordered structure carrier, can prepare catalyst provided by the invention.The method of described coating can be that water is coated with method, infusion process or spray process.The concrete operations of coating can be carried out with reference to the method described in CN1199733C.The temperature of described coating is preferably 10-70 DEG C, is more preferably 15-35 DEG C, and the pressure of coating is preferably-0.04 MPa to 0.4 MPa, and coating time is preferably 0.1-100 second.
According to the present invention, the ordered structure carrier of good for coating described active component coating slurries is carried out drying and roasting.The method of described drying and condition are conventionally known to one of skill in the art, such as, dry method can be dry, dry, forced air drying.Under preferable case, in step (3), dry temperature can be room temperature to 300 DEG C, is preferably 100-200 DEG C; The time of described drying is at least 0.5 hour, is preferably 1-10 hour.
According to the present invention, the condition of roasting described in step (3) also can be conventionally known to one of skill in the art, and in general, the temperature of described roasting is 400-800 DEG C, is preferably 500-700 DEG C; The time of described roasting is at least 0.5 hour, is preferably 1-10 hour.
According to the present invention, the kind of described molecular sieve is described in detail aforementioned, does not repeat them here.
According to the present invention, when described matrix is silica, substrate source can be silica source, and preferred described silica source is the natural crystal that silica or silica content are greater than 45 % by weight.Preferably, described silica source can be at least one in Ludox, laminated clay column, diatomite, expanded perlite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.
According to the present invention, when described matrix is aluminium oxide, substrate source can be alumina source, and described alumina source can for changing the material of aluminium oxide under the condition of the described roasting of step (3).Preferably, described alumina source is one or more in boehmite, hydrated alumina and Alumina gel; Described hydrated alumina is at least one in boehmite, false boehmite, hibbsite and amorphous hydroted alumina.
Present invention also offers the catalyst obtained by method provided by the invention.
According to the present invention, this catalyst comprises ordered structure carrier and is distributed in the active component coating of ordered structure carrier inner surface and/or outer surface; With the gross weight of described catalyst for benchmark, the content of described active component coating is 10-50 % by weight; With the gross weight of described active component coating for benchmark, described active component coating is 5-50 % by weight containing the total content of silica and aluminium oxide, and the content of molecular sieve is 50-95 % by weight; Described molecular sieve is the molecular sieve with ten-ring one dimension ellipse pore passage structure.Total content preferably containing silica and aluminium oxide is 5-20 % by weight, and the content of molecular sieve is 80-95 % by weight.
Present invention also offers a kind of method that naphtha catalytic cracking produces propylene, the method comprises: under naphtha catalytic cracking reaction condition, by naphtha and water and catalyst exposure, obtains propylene product, wherein, described catalyst comprises catalyst provided by the invention.
According to the present invention, under preferable case, described naphtha catalytic cracking reaction condition comprises: temperature is 520-590 DEG C, and pressure is 0.1-0.2MPa, and water/oily feed weight, than being 0.3-2, is preferably 0.4-1.7; Catalyst is in active component coating, and naphtha feed weight (hourly) space velocity (WHSV) is 2-40h
-1, be preferably 2.3-36.5h
-1.
According to the present invention, under preferable case, described naphtha contains the alkene of 0.5-1.5 % by weight, the alkane of 40-60 % by weight, the cycloalkane of 20-40 % by weight and 10-20 % by weight aromatic hydrocarbons.
Below will be described the present invention by embodiment.
In following examples, gas-phase product character is by gas chromatography, adopts the Instrument measuring of Agilent company HP6890 model.Yield and selectively to be obtained by following formulae discovery:
Yield=(object product (C
2 =+ C
3 =) growing amount/reaction-ure feeding amount) × 100%
Selective=(object product (C
2 =~ C
4 =) growing amount/reactant inversion quantity) × 100%
Embodiment 1
The preparation method of the present embodiment for illustration of catalyst provided by the invention and the method for naphtha catalytic cracking product propylene.
(1) Kaolinite Preparation of Catalyst.Mixed with 56.2 grams of deionized waters by 56.2 grams of ZSM-22 molecular sieves (Nanjing Ji Cang nanosecond science and technology Co., Ltd, Si/Al mol ratio=30:1), wet ball grinding becomes molecular sieve pulp, sieve particle diameter d
90=10 microns, solid content is 50 % by weight.28.4 grams of Alumina gel (salic 22 % by weight are added in slurries, catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces), stir 10 minutes, add polyglycol solution 1.5 grams (in polyglycol solution, polyethylene glycol percetage by weight is 2 % by weight), stir and within 20 minutes, obtain catalyst coat and prepare mix slurry (coating slurry).
By active component coating slurries, (carrier hole density is 100 holes/square centimeter to coating cordierite honeycomb carrier, the sectional area in each hole is 7 square millimeters, percent opening is 80%, the shape in hole is square), at 120 DEG C, roasting 5 hours at dry 5 hours and 500 DEG C, obtains catalyst, wherein, active component coating content is 15 % by weight.
By the calculated activity component coating composition that feeds intake: ZSM-22 molecular sieve content is 90 % by weight, and matrix (aluminium oxide) content is 10 % by weight.
(2) propylene is produced.By catalyst obtained to (1) as beds, form monolithic reactors, wherein the gross weight of active component coating is 62.5 grams.Naphtha (containing alkene 1 % by weight, containing alkane 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, basic nitrogen 0.5 μ g/g) and water are injected above-mentioned monolithic reactors after 250 DEG C of preheatings.The weight (hourly) space velocity (WHSV) (weight of naphtha is relative to the gross weight of active component coating) that wherein naphtha injects is 2.3hr
-1, water/oily feed weight ratio is 0.46.Reaction temperature is 520 DEG C, and pressure is 0.1MPa.Reaction result is in table 1.
Embodiment 2
The preparation method of the present embodiment for illustration of catalyst provided by the invention and the method for naphtha catalytic cracking product propylene.
(1) Kaolinite Preparation of Catalyst.
Mixed with 20 grams of deionized waters by 32 grams of ZSM-23 zeolite powders (self-control, Si/Al mol ratio=50:1), wet ball grinding becomes slurries, slurries Middle molecule sieve particle diameter d
90=8 microns; In slurries, add 150 grams of peptization boehmites (salic 18 % by weight, pH value is 2.8, catalyst asphalt in Shenli Refinery of China Petrochemical Industry product), stir 15 minutes; Add polyacrylic acid solution 3.2 grams (in polyacrylic acid solution, polyacrylic acid percetage by weight is 1 % by weight), stir 30 minutes, obtain catalyst coat mix slurry.
By active component coating slurries, (carrier hole density is 80 holes/square centimeter to coating cordierite honeycomb carrier, the sectional area in each hole is 5 square millimeters, percent opening is 60%, the shape in hole is circular), at 120 DEG C, roasting 5 hours at dry 5 hours and 500 DEG C, obtains catalyst, wherein, active component coating content is 20 % by weight.
By the calculated activity component coating composition that feeds intake: ZSM-23 zeolite content is 54 % by weight, and matrix (aluminium oxide) content is 46 % by weight.
(2) propylene is produced.By catalyst obtained to (1) as beds, form monolithic reactors, wherein, the gross weight of active component coating is 59 grams.Naphtha (containing alkene 1 % by weight, containing alkane 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, basic nitrogen 0.4 μ g/g) and water are injected above-mentioned monolithic reactors after 250 DEG C of preheatings.Wherein, the weight (hourly) space velocity (WHSV) (gross weight relative to active component coating) that naphtha injects is 36.5hr
-1, water/oily feed weight ratio is 0.96.Reaction temperature is 570 DEG C, and pressure is 0.1MPa.Reaction result is in table 1.
Embodiment 3
The preparation method of the present embodiment for illustration of catalyst provided by the invention and the method for naphtha catalytic cracking product propylene.
(1) Kaolinite Preparation of Catalyst.Mixed with 60 grams of distilled water by 70 grams of NU-10 zeolites (self-control, Si/Al mol ratio=80:1), wet ball grinding becomes slurries, slurries Middle molecule sieve particle diameter d
90=5 microns; In slurries, add 143 grams of acidic silicasols (silicon oxide-containing 21 % by weight, catalyst asphalt in Shenli Refinery of China Petrochemical Industry product), stir 60 minutes; Add polyethylene glycol and polyacrylic acid mixed solution 12.6 grams (polyethylene glycol and polyacrylic acid percetage by weight are respectively 3 % by weight and 5 % by weight), stir and within 30 minutes, obtain catalyst coat and prepare mix slurry.
By active component coating slurries, (carrier hole density is 20 holes/square centimeter to coating cordierite honeycomb carrier, the sectional area in each hole is 2 square millimeters, percent opening is 75%, the shape in hole is circular), at 120 DEG C, roasting 5 hours at dry 5 hours and 500 DEG C, obtains catalyst, wherein, active component coating content is 30 % by weight.
By the calculated activity component coating composition that feeds intake: NU-10 zeolite content is 70 % by weight, and matrix (silica) content is 30 % by weight.
(2) propylene is produced.By catalyst obtained to (1) as beds, form monolithic reactors, wherein, the gross weight of active component coating is 100 grams.Naphtha (containing alkene 1 % by weight, containing alkane 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, basic nitrogen 0.6 μ g/g) and water are injected above-mentioned monolithic reactors after 250 DEG C of preheatings.Wherein, the weight (hourly) space velocity (WHSV) (weight of naphtha is relative to the gross weight of active component coating) that naphtha injects is 4.6hr
-1, water/oily feed weight ratio is 1.61.Reaction temperature is 590 DEG C, and pressure is 0.2MPa.Reaction result is in table 1.
Embodiment 4
According to the method cracking naphtha of embodiment 3, unlike, catalyst Middle molecule sieve is replaced by ZSM-22 zeolite (sial atomic molar ratio is 30) and ISI-4 zeolite (sial atomic molar ratio is 30), and the part by weight of the two is 1:1.
Embodiment 5
According to the method cracking naphtha of embodiment 3, unlike, catalyst Middle molecule sieve is replaced by NU-10 zeolite (sial atomic molar ratio is 80) and ZSM-23 zeolite (sial atomic molar ratio is 50), and the part by weight of the two is 2:1.
Embodiment 6
According to the method cracking naphtha of embodiment 3, unlike, catalyst Middle molecule sieve is replaced by SSZ-32 zeolite (sial atomic molar ratio is 30) and KZ-1 zeolite (sial atomic molar ratio is 50), and the part by weight of the two is 5:1.
Embodiment 7
According to the method cracking naphtha of embodiment 4, unlike, catalyst Middle molecule sieve ZSM-22 zeolite is by ZSM-22 zeolite (sial atomic molar ratio is 30) and NU-10 zeolite (sial atomic molar ratio is 30), and the weight ratio of the two is 3:1; ISI-4 zeolite is replaced by the mixture of ISI-4 zeolite (sial atomic molar ratio is 30) and ZSM-23 zeolite (sial atomic molar ratio is 30), and the weight ratio of the two is 4:1.
Comparative example 1
(1) Kaolinite Preparation of Catalyst.Mixed with 56.2 grams of deionized waters by 56.2 grams of ZSM-5 zeolites (Nankai University produces, Si/Al mol ratio=30:1), wet ball grinding becomes molecular sieve pulp, sieve particle diameter d
90=10 microns, solid content is 50 % by weight.In slurries, add 28.4 grams of Alumina gel (salic 22 % by weight, catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces), stir and obtain mix slurry through extruded moulding in 20 minutes.
By the calculated activity component coating composition that feeds intake: ZSM-5 zeolite content is 90 % by weight, and matrix (aluminium oxide) content is 10 % by weight.
(2) propylene is produced.By catalyst obtained to (1) as beds, form fixed bed reactors.Naphtha (containing alkene 1 % by weight, containing alkane 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, basic nitrogen 0.5 μ g/g) and water are injected above-mentioned fixed bed reactors after 250 DEG C of preheatings.The weight (hourly) space velocity (WHSV) (gross weight relative to beds) that wherein naphtha injects is 4.6hr
-1, water/oily feed weight ratio is 1.61.Reaction temperature is 590 DEG C, and pressure is 0.1MPa.Reaction result is in table 1.
Comparative example 2
According to the method for embodiment 1, unlike, the catalyst of use is that the particle diameter containing the ZSM-22 zeolite (sial atomic molar ratio is 30) of 18 % by weight and the matrix (aluminium oxide) of 82 % by weight is 2mm, length is the bar shaped catalyst of 5mm.
Calculate (C
2 =+ C
3 =) yield and (C
2 =~ C
4 =) selective, the results are shown in Table 1.
Comparative example 3
According to the method for embodiment 1, unlike, in ordered structure catalyst, the molecules of active components sieve of active component coating is Beta zeolite (sial atomic molar ratio is 30), and all the other are all identical.
Calculate (C
2 =+ C
3 =) yield and (C
2 =~ C
4 =) selective, the results are shown in Table 1.
Table 1
As can be seen from the data result of table 1, catalyst provided by the invention adopts ordered structure carrier and containing the molecular sieve with ten-ring one dimension ellipse pore passage structure, the active component coating of TON or MTT structure, carrying out in naphtha catalytic cracking product propylene, high ethene and propene yield can be obtained, and wherein propylene/ethylene ratio is greater than 1, can realize producing more propylene.
Claims (16)
1. naphtha catalytic cracking produces a catalyst for propylene, and this catalyst comprises: ordered structure carrier and the active component coating being distributed in ordered structure carrier inner surface and/or outer surface; With the gross weight of described catalyst for benchmark, the content of described active component coating is 10-50 % by weight; With the gross weight of described active component coating for benchmark, described active component coating contains the molecular sieve of 50-95 % by weight and the matrix of 5-50 % by weight; Described molecular sieve is the molecular sieve with ten-ring one dimension ellipse pore passage structure.
2. catalyst according to claim 1, wherein, described molecular sieve is the molecular sieve of TON structure and/or the molecular sieve of MTT structure.
3. catalyst according to claim 2, wherein, described molecular sieve is the mixture of the molecular sieve of TON structure and the molecular sieve of MTT structure; Preferably, the weight ratio of the molecular sieve of described TON structure and the molecular sieve of MTT structure is 0.1-10:1, is more preferably 1-5:1; The molecular sieve of described TON structure comprise in Theta-1 zeolite, ISI-1 zeolite, KZ-2 zeolite, NU-10 zeolite, ZSM-22 zeolite and SSZ-32 zeolite one or more; The molecular sieve of described MTT structure comprise in ZSM-23 zeolite, EU-13 zeolite, ISI-4 zeolite and KZ-1 zeolite one or more.
4. catalyst according to claim 3, wherein, the molecular sieve of described TON structure is the mixture of ZSM-22 zeolite and NU-10 zeolite, and the weight ratio of the two is 2-5:1; The molecular sieve of described MTT structure is the mixture of ISI-4 zeolite and ZSM-23 zeolite, and the weight ratio of the two is 2-5:1.
5., according to the catalyst in claim 1-4 described in any one, wherein, with the gross weight of described active component coating for benchmark, described active component coating contains the molecular sieve of 54-90 % by weight and the matrix of 10-46 % by weight.
6., according to the catalyst in claim 1-4 described in any one, wherein, with the gross weight of described catalyst for benchmark, the content of described active component coating is 15-30 % by weight.
7. catalyst according to claim 1, wherein, described ordered structure carrier is selected from the monolithic substrate of the parallel channels structure with both ends open.
8. catalyst according to claim 7, wherein, the hole density in the cross section of described ordered structure carrier is 6-140 hole/square centimeter, and the sectional area in each hole is 0.4-10 square millimeter, and percent opening is 50-80%.
9. according to the catalyst in claim 1,7 and 8 described in any one, wherein, described ordered structure carrier is selected from least one in cordierite honeycomb carrier, mullite honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrate.
10. according to the catalyst in claim 1-4 described in any one, wherein, described matrix is selected from least one in aluminium oxide, silica, amorphous aluminum silicide, zirconia, titanium oxide, boron oxide and alkaline earth oxide.
11. 1 kinds of naphtha catalytic crackings prepared in claim 1-10 described in any one produce the method for the catalyst of propylene, and the method comprises:
(1) molecular sieve and aqueous solvent mixed and grind, obtaining molecular sieve pulp, described molecular sieve is the molecular sieve with ten-ring one dimension ellipse pore passage structure;
(2) described molecular sieve pulp is mixed with substrate source, form active component coating slurries;
(3) with the also dry and roasting of described active component coating slurries coating ordered structure carrier.
12. methods according to claim 11, wherein, in step (1), the sieve particle diameter d in described molecular sieve pulp
90for 1-10 micron, the solid content of described molecular sieve pulp is 15-70 % by weight, and described aqueous solvent is water.
13. methods according to claim 11, wherein, active component coating slurries described in step (2) are also containing dispersant, and the weight ratio of described dispersant and described molecular sieve is less than 0.2 and is greater than 0.
14. catalyst obtained by the method in claim 11-13 described in any one.
15. 1 kinds of naphtha catalytic crackings produce the method for propylene, the method comprises: under naphtha catalytic cracking reaction condition, by naphtha and water and catalyst exposure, obtains propylene product, it is characterized in that, described catalyst comprises the catalyst in claim 1-10 and 14 described in any one.
16. methods according to claim 15, wherein, described naphtha catalytic cracking reaction condition comprises: temperature is 520-590 DEG C, and pressure is 0.1-0.2MPa, and water/oily feed weight is than being 0.3-2; Catalyst is in active component coating, and naphtha feed weight (hourly) space velocity (WHSV) is 2-40h
-1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1986058A (en) * | 2005-12-22 | 2007-06-27 | 中国石油化工股份有限公司 | Catalyst in regular structure and its preparing method |
| US20100105974A1 (en) * | 2008-10-24 | 2010-04-29 | Towler Gavin P | Mixture of Catalysts for Cracking Naphtha to Olefins |
| CN102451742A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method for honeycomb supported catalyst containing coating of molecular sieve composition |
| CN102451731A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation and application of coating slurry for cellular carrier catalyst |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1986058A (en) * | 2005-12-22 | 2007-06-27 | 中国石油化工股份有限公司 | Catalyst in regular structure and its preparing method |
| US20100105974A1 (en) * | 2008-10-24 | 2010-04-29 | Towler Gavin P | Mixture of Catalysts for Cracking Naphtha to Olefins |
| CN102451742A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method for honeycomb supported catalyst containing coating of molecular sieve composition |
| CN102451731A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation and application of coating slurry for cellular carrier catalyst |
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