CN102451742A - Preparation method for honeycomb supported catalyst containing coating of molecular sieve composition - Google Patents
Preparation method for honeycomb supported catalyst containing coating of molecular sieve composition Download PDFInfo
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- CN102451742A CN102451742A CN2011100745735A CN201110074573A CN102451742A CN 102451742 A CN102451742 A CN 102451742A CN 2011100745735 A CN2011100745735 A CN 2011100745735A CN 201110074573 A CN201110074573 A CN 201110074573A CN 102451742 A CN102451742 A CN 102451742A
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Abstract
The invention provides a preparation method for a honeycomb supported catalyst containing a coating of a molecular sieve composition. The method comprises the step of coating a honeycomb support with coating slurry, wherein, the coating slurry comprises a molecular sieve, phosphorus and aluminum components, a dispersant and water, on the basis of the weight of the coating slurry, the content of the molecular sieve in the slurry is 3 to 60 wt %, the weight ratio of the phosphorus and aluminum components to the molecular sieve is 0.1-30:100, the weight ratio of the dispersant to the molecular sieve is 0-20:100, the weight of the phosphorus and aluminum components is counted on the basis of total weight of P2O5 and Al2O3, the weight of the molecular sieve is counted in terms of a dry basis, the dispersant is one compound or more compounds containing polyhydroxy groups, polyoxyethylene groups or polycarboxylic groups, the particle diameter of the phosphorus and aluminum components is less than 100 nm, and the particle diameter d90 of the molecular sieve is 1 to 10 mu m. The honeycomb supported catalyst containing the molecular sieve composition in the invention has a firm coating.
Description
Technical field
The present invention relates to a kind of honeycomb substrate method for preparing catalyst that comprises the combination of molecular sieve coating.
Background technology
Molecular sieve is important heterogeneous catalytic reaction catalysis material, is widely used in petroleum refining and processing, petrochemical industry and the fine chemistry industry production process.In use normally molecular sieve or combination of molecular sieve are processed certain grain shape, for example be applied to the bar shaped beaded catalyst of particles filled bed, be applied to the microspherical catalyst of fluid bed.The honeycomb substrate catalyst of load molecular sieve component begins aspect Industrial Catalysis, to be applied in recent years; This catalyst generally includes honeycomb substrate and molecular sieve component (molecular sieve or contain the composition of molecular sieve) load layer; Wherein honeycomb substrate is the integral blocks that moulding prepares; Its inside has long, straight-through duct, and molecular sieve component loads on the interior and/or outer wall in duct.A kind of method at load molecular sieve on the honeycomb substrate is in the synthetic crystallization of molecular sieve, to put into honeycomb substrate, and synthetic reaction finishes, on the duct inwall in the carrier " growth " go out molecular sieve layer.Method commonly used is that molecular sieve component is carried on the honeycomb substrate through the method that applies.For example CN100448947C discloses a kind of method that reduces olefin(e) centent in the gasoline, and wherein used catalyst comprises honeycomb support and is distributed in the lip-deep combination of molecular sieve coating of honeycomb support.This Preparation of catalysts method is first preparation combination of molecular sieve particle, again the composition grain ball milling is become slurries and adds surfactant-modifiedly, or uses the surfactant solution modified support earlier, applies combination of molecular sieve then to the honeycomb substrate duct.But this patent active component coating use floating coat is easy to come off, and is difficult to improve the content of molecular sieve in the coating, and the gasoline activity of conversion is not high.
Summary of the invention
The technical problem that the present invention will solve provides a kind of honeycomb substrate method for preparing catalyst that comprises the combination of molecular sieve coating; The catalyst coat of this method preparation is more firm, and the other technical problem that the present invention will solve provides a kind of coating slurries that are used for this method and preparation method thereof.
The present invention provides a kind of honeycomb substrate method for preparing catalyst that comprises the combination of molecular sieve coating, comprises the step that applies honeycomb substrate with the coating slurries; Wherein, said coating slurries comprise molecular sieve, phosphorus al compsn and water, contain or do not contain dispersant, are benchmark with the weight of coating slurries, and the content of molecular sieve is 3～60 weight % in the said coating slurries, and the phosphorus al compsn is (with P
2O
5And Al
2O
3The gross weight meter) weight ratio with molecular sieve (in butt weight) is 0.1～30: 100, and the weight ratio of dispersant and molecular sieve is 0～20: 100; Said dispersant is selected from one or more in the compound that polyhydroxy, polycarboxylic acids base or polyoxyethylene groups are arranged in the molecule, and the particle diameter of said phosphorus al compsn is less than 100nm, and said sieve particle diameter d 90 is 1～10 micron.
The present invention also provides a kind of above-mentioned coating slurries that comprise the honeycomb substrate method for preparing catalyst of combination of molecular sieve coating that are used for, and said coating slurries comprise molecular sieve, phosphorus al compsn and water, contain or do not contain dispersant; Wherein, be benchmark with the gross weight of combination of molecular sieve coating slurries, the content of molecular sieve is 3～60 weight % in the said slurries, the phosphorus al compsn is (with P
2O
5And Al
2O
3The gross weight meter) weight ratio with molecular sieve (in butt weight) is 0.1～30: 100; The weight ratio of dispersant and molecular sieve (in butt weight) is 0～20: 100; Said dispersant is selected from one or more in the compound that polyhydroxy or polyoxyethylene groups are arranged in the molecule; Said sieve particle diameter d 90 is 1～10 micron, and the particle diameter of phosphorus al compsn is no more than 100nm.
The present invention also provides a kind of preparation method of coating slurries, may further comprise the steps:
(1) molecular sieve is mixed with water, grind, obtain sieve particle diameter (d90) and be 1～10 micron molecular sieve pulp;
(2) molecular sieve pulp, the particle diameter with step (1) mixes less than 100nm phosphorus al compsn and dispersant solution, obtains the coating slurries.
Honeycomb substrate method for preparing catalyst provided by the invention is prepared into a kind of coating slurries that contain sieve particle, phosphorus al compsn, dispersant and water with molecular sieve earlier, loads on the duct inwall of honeycomb substrate through coating processes then; Form the combination of molecular sieve coating, said combination of molecular sieve coating is firm, difficult drop-off in the use; Can obtain the good catalyst coat of fastness; Molecular sieve content is high in the coating, good catalyst activity, and the medium property influence is few; Molecular sieve content can reach 75～99 weight % in the coating of prepared catalyst, and phosphorous oxide and alumina content are 1～25 weight %.Provided by the invention minute coating slurry preparation method; Can prepare the coating slurries that are applicable to above-mentioned honeycomb substrate Preparation of Catalyst; These slurries load on the catalyst coat that forms on the inwall of duct, and have good fastness between cell walls, are difficult in the catalyst use chapping and coming off.
The specific embodiment
In the honeycomb substrate method for preparing catalyst that contains the combination of molecular sieve coating provided by the invention; Preferably include molecular sieve, phosphorus al compsn, dispersant solution and water in the described coating slurries; Gross weight with the coating slurries is a benchmark; In the butt molecular sieve content is 3～60 weight %, is preferably 5～55 weight %; The phosphorus al compsn is (with P
2O
5And Al
2O
3The gross weight meter) is 0.1～30: 100 with the weight ratio of molecular sieve (in butt weight), is preferably 0.3～25: 100, more preferably 5～25: 100; The weight ratio of dispersant and molecular sieve is 0.01～20: 100, is preferably 0.05～18: 100.Can also contain clay in the coating slurries of the present invention, the weight ratio of described clay and molecular sieve is 0～100: 100; In the slurries, the total content of clay and molecular sieve is 3～60 weight %.Wherein said phosphorus al compsn is a particle diameter less than the phosphorus aluminium glue of 100nm and/or the particle diameter presoma material less than the formed phosphorus aluminium glue of 100nm; The particle diameter of said phosphorus al compsn is preferably 1～90nm; 1～60nm more preferably; Mean particle diameter is preferably 5～70nm, more preferably 5～30nm.
In the honeycomb substrate method for preparing catalyst that contains the combination of molecular sieve coating provided by the invention, said coating slurries are the method preparation through may further comprise the steps preferably:
(1) molecular sieve is mixed with water, grind, obtain sieve particle diameter d 90 and be 1～10 micron molecular sieve pulp;
(2) molecular sieve pulp that step (1) is obtained, phosphorus aluminium glue and/or presoma material and the dispersant solution that can form the phosphorus aluminium glue mix, and add or do not add clay; Wherein, the content of dispersant is 1～10 weight % in the dispersant solution, and the particle diameter of phosphorus aluminium glue and the presoma material that can form the phosphorus aluminium glue is all less than 100nm; Be preferably 1～90nm; More preferably 1～60nm, mean particle diameter is preferably 5～70nm, more preferably 5～30nm.
Wherein, step is mixed molecular sieve in (1) with water, grinds then and obtains molecular sieve pulp, and said grinding can be adopted any existing method, for example can adopt wet ball grinding, and it is 1～10 micron that said grinding makes the d90 of sieve particle diameter in the slurries; Be preferably 4～8 microns, can make the cracking gasoline reforming catalyst of preparation have higher alkene activity of conversion and propylene selectivity, and coating have fastness preferably.Described water is deionized water, decationized Y sieve water or distilled water.The d90 value that wherein said particle diameter d90 is a particle size distribution, its implication: diameter accounts for 90% of sieve particle cumulative volume in the slurries less than the volume of the sieve particle of this value (d90) in the slurries.
Can molecular sieve pulp, phosphorus al compsn (phosphorus aluminium glue and/or can form the presoma material of phosphorus aluminium glue) and dispersant solution be mixed through any existing method in the step (2); Preferable methods is: in the molecular sieve pulp that step (1) obtains, add the phosphorus al compsn, stir, preferred mixing time was at least 5 minutes; Preferred mixing time is 15～120 minutes; Add dispersant solution then and stir, preferred, stirred 10～60 minutes behind the adding dispersant solution.Described phosphorus aluminium glue and the particle diameter of presoma material that can form the phosphorus aluminium glue are preferably 1～90nm all less than 100nm, more preferably 1～60nm, and mean particle diameter all is preferably 5～70nm, more preferably 5～30nm.Described phosphorus aluminium glue is phosphorus aluminium colloidal sol and/or phosphorus alumina gel for example; The described presoma material that forms the phosphorus aluminium glue is for forming the phosphorous oxide source and the alumina source of phosphorus aluminium glue; Described phosphorous oxide source is acid phosphorus colloidal sol or SPA for example; Said alumina source for example can by the aluminium hydroxide of sour peptization, can be by in the aluminium oxide of sour peptization or the aluminium colloidal sol one or more, described can be in ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-aluminium oxide, δ-aluminium oxide, the θ-aluminium oxide one or more by the aluminium oxide of sour peptization: said can be in gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite, the boehmite one or more by the aluminium hydroxide of sour peptization; The concentration of said SPA preferably is not less than 85 weight %.Preferably, the described presoma material that forms the phosphorus aluminium glue is for can be by the aluminium hydroxide of sour peptization and/or can be by the aluminium oxide of sour peptization and phosphoric acid or acid phosphorus colloidal sol and aluminium colloidal sol.When comprising clay in the described coating slurries; Said clay preferably added before dispersant; The d90 that more preferably before the phosphorus al compsn, adds said clay slurry medium clay soil is 1～10 micron; Be preferably 4～8 microns, said clay can be selected from kaolin, halloysite, imvite, phosphorus algae soil, tired in the soil one or more, the preferred kaolin of taking off.
In the step (2), preferred, the adding weight of described dispersant solution is 0.01～20 weight % of molecular sieve butt weight, and preferred addition is 0.05～18 weight % of molecular sieve butt weight; Wherein the content of dispersant is 1～10 weight % in the dispersant solution.Said dispersant solution can prepare through following method:, add 9～99 parts by weight of deionized water and make the dispersant dissolving as 1 weight portion with dispersant, the percetage by weight of dispersant is 1～10 weight % in the dispersant solution.Described dispersant is selected from the compound that polyhydroxy or polyoxyethylene groups active group are arranged in all more stable molecule of bronsted lowry acids and bases bronsted lowry one or more; For example for being in polyalcohol type, polyoxyethylene-type or the polycarboxylic acids fundamental mode compound one or more; Preferably, said dispersant is one or more in polyethylene glycol, glycerine, polyvinyl alcohol or the polyacrylic acid.
In the honeycomb substrate method for preparing catalyst that contains the combination of molecular sieve coating provided by the invention, said molecular sieve can be a large pore zeolite, one or more in mesopore zeolite and the non-zeolite molecular sieve.Said large pore zeolite refers to that its pore structure ring opening is at least the zeolite of 0.7 nanometer; It can be selected from y-type zeolite, rare earth Y type zeolite (REY), baked rare earth Y type zeolite (CREY), ultrastable (USY), L zeolite, Beta zeolite, modenite and the ZSM-18 zeolite one or more, is preferably in y-type zeolite, rare earth Y type zeolite, baked rare earth Y type zeolite, ultrastable and the Beta zeolite one or more.Said mesopore zeolite refers to the zeolite of its cavernous structure opening in the 0.56-0.70 nanometer; It can be selected from ZSM-5 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, the MCM-56 zeolite one or more, preferred ZSM-5 zeolite.Said non-zeolite molecular sieve is selected from one or more in phosphorus aluminate or phosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO) that phosphate (like metal phosphate metallosilicate, titanium phosphate titanosilicate) with different phosphate aluminum ratio, metal aluminate metalloaluminates (like germanium aluminate germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphate metalloaluminophosphates, metal combines, aluminophosphates silicoaluminophosphates (SAPO), the gallium germanate (gallogermanates), is preferably the SAPO-11 molecular sieve.
In the honeycomb substrate method for preparing catalyst that contains the combination of molecular sieve coating provided by the invention; Describedly apply honeycomb substrate, can carry out, comprise the coating slurries are contacted with honeycomb substrate according to existing method with the coating slurries; Make described coating slurries be full of all ducts of honeycomb substrate; Blow off the carrier outer surface with compressed air then, drying, the step of roasting.Described drying can adopt the mode of oven dry, for example dries 2～5 hours preferred 600～700 ℃ of the temperature of said roasting, preferred 1～3 hour of roasting time down at 100～120 ℃.Obtain containing the honeycomb substrate catalyst of combination of molecular sieve coating after the roasting.Wherein saidly blow off the method for carrier outer surface with compressed air, can be according to existing method, for example CN1191127C disclosed method.Said honeycomb substrate can select for use commercially available composite oxides honeycomb substrate for example cordierite carrier also can select the honeycomb substrate of metal material for use.
The honeycomb substrate method for preparing catalyst that comprises the combination of molecular sieve coating provided by the invention; Prepared catalyst; Coating is firm, is difficult for chapping and coming off, and can be used to prepare the honeycomb substrate catalyst that comprises macromolecule sieve content coating; Molecular sieve content can be preferably 75～99 weight % up to 70～99.7 weight % in the said combination of molecular sieve coating.Propylene honeycomb substrate catalyst is produced in the gasoline catalyzing cracking that is used for of the inventive method preparation, and propene yield is high, and selectivity is good, and the olefin conversion in the gasoline is high.
Following embodiment further specifies wherein used dispersant to the present invention: polyacrylic acid is a α reagent Company products, and molecular weight 24000 is analyzed pure; Polyethylene glycol, the degree of polymerization 2000, Shanghai chemical reagents corporation of traditional Chinese medicines group, chemical pure; Glycerine, analyze pure, Shanghai chemical reagents corporation of traditional Chinese medicines group.Phosphorus al compsn particle diameter Determination of distribution method adopts light correlation spectroscopy (PCS), and referring to ASTME2490, the measuring method of sieve particle diameter adopts the laser particle analyzer method, referring to ASTMD4464-00 (2005).
Instance 1
With 108 grams (in butt, down together) HY type molecular sieve powder (d90=14 micron, technical grade; Catalyst Shandong branch company of China Petrochemical Industry product) mixes with 120.5 gram deionized waters; Wet ball grinding becomes molecular sieve pulp, and sieve particle diameter d 90=5 micron adds 128 gram phosphorus aluminium glues (preparation method: with boehmite and the making beating of decationizing water in slurries; Adding concentration under stirring is the SPA of 85 weight %, is warming up to 70 ℃ of reactions and makes in 1 hour.Wherein contain phosphorous oxide 18 weight %, aluminium oxide 3 weight %, the pH value is 1.2; Particle diameter is 27～55nm, and average grain diameter is 32nm), the addition of phosphorus aluminium glue is 25 weight % of molecular sieve weight; Stirred 10 minutes, and added polyglycol solution 3.24 grams (percetage by weight of polyethylene glycol is 2 weight %), the addition of this solution is 3 weight % of molecular sieve weight; Stir and obtained catalyst coat in 20 minutes and prepare mix slurry (coating slurries), molecular sieve content is 30 weight % in the slurries.
Prepare mix slurry with prepared catalyst coat and apply honeycomb substrate (cordierite honeycomb carrier, 31 hole/square centimeters, non-metal chemical mechinery works, Yixing, Jiangsu honeycomb pottery subsidiary factory product; All duct inner surfaces down together); Blow off the carrier outer surface with compressed air (pressure is 0.4MPa, down together), dried 2 hours down for 120 ℃; 650 ℃ of following roastings 1 hour obtain having the honeycomb structured catalyst configurations of molecular sieve catalyst coating.
Using flow velocity is the duct 5 minutes that the honeycomb structured catalyst configurations that obtains is swept in 10 meter per second normal temperature (25 ℃) air wind, weighs, and obtains the weight that normal temperature air purges the back honeycomb structured catalyst configurations; Using flow velocity then is 10 meter per seconds, and temperature is to weigh in the duct of the honeycomb structured catalyst configurations that obtains of 400 ℃ warm air blowoff in 5 minutes, obtains the weight of honeycomb structured catalyst configurations after the warm air blowoff.The weight of honeycomb structured catalyst configurations and the catalyst loss amount behind the purging are listed in the table 1 after weight that the weight of honeycomb structured catalyst configurations, normal temperature air purge back honeycomb structured catalyst configurations behind the weight of the honeycomb substrate of uncoated catalyst coat (carrier bare weight), the coating supported catalyst and the warm air blowoff.
Instance 2
With 120 gram rare earth Y type molecular sieve powder (d90=12 micron, RE
2O
3Content 3 weight %, catalyst Shandong branch company of China Petrochemical Industry product) mix with 261 gram deionized waters, wet ball grinding becomes slurries, sieve particle diameter d 90=8 micron in the slurries; (with gama-alumina and the making beating of decationizing water, adding concentration under stirring is the SPA of 85 weight %, is warming up to 60 ℃ of reactions and makes after 1 hour in slurries, to add 96 gram phosphorus aluminium glues; Wherein contain phosphorus pentoxide 10 weight %, aluminium oxide 5 weight %, the pH value is 2.0, particle diameter is 43～72nm, average grain diameter is 58nm), with P
2O
5And Al
2O
3Gross weight meter phosphorus aluminium glue addition be 12 weight % of molecular sieve weight, stirred 15 minutes; Add polyacrylic acid solution 12 grams (polyacrylic acid content is 1 weight %), the polyacrylic acid solution addition is 10 weight % of molecular sieve weight, stirs 30 minutes, obtains the catalyst coat slurries, and wherein molecular sieve content is 25 weight %.Gained catalyst coat slurries are full of all ducts of honeycomb substrate (said honeycomb substrate is with embodiment 1), blow off the carrier outer surface, 120 ℃ of oven dry 2.5 hours down, 650 ℃ of following roastings 2.5 hours with compressed air.
The method purging honeycomb catalyst of describing according to instance 1 carries out the deflation experiment, and the result lists in the table 1.
Instance 3
With 180 gram HZSM-5 type molecular sieve powder (silica alumina ratio is 60 for d90=14 micron, catalyst Shandong branch company of China Petrochemical Industry product), mix with 87.6 gram distilled water, wet ball grinding becomes slurries, sieve particle diameter d 90=5 micron in the slurries; (the SB aluminium hydrate powder that German Condex company is produced with the making beating of decationizing water, stirs that to add concentration down be the SPA of 85 weight %, is warming up to 65 ℃ of reactions and makes in 1 hour in slurries, to add 60 gram phosphorus aluminium glues; Wherein contain phosphorous oxide 12 weight %, aluminium oxide 3 weight %, the pH value is 1.6, particle diameter is 13～35nm, average grain diameter is 24nm), phosphorus aluminium glue addition is 5 weight % of molecular sieve weight, stirs 60 minutes; Add polyethylene glycol and restrain (polyethyleneglycol content is 3 weight %, and polyacrylic acid content is 5 weight %) with polyacrylic acid mixed solution 32.4, the solution addition is 18 weight % of molecular sieve weight, stirs to obtain catalyst coat in 30 minutes and prepare mix slurry.Resulting catalyst coat is prepared all ducts that mix slurry is full of honeycomb substrate, blow off the carrier outer surface, 120 ℃ of down oven dry 1.5 hours, 650 ℃ of following roastings 2 hours with compressed air.
The method purging honeycomb catalyst of describing according to instance 1 carries out the deflation experiment, and the result lists in the table 1.
Instance 4
With 100 gram DASY0.0 type molecular sieve powder (d90=14 microns; Catalyst Shandong branch company of China Petrochemical Industry product) and 50 gram beta molecular sieve powder (d90=14 microns; Catalyst Shandong branch company of China Petrochemical Industry product); Mix with deionized water 913.5 grams, wet ball grinding becomes slurries, the particle diameter d90=5 micron of molecular sieve in the slurries; Adding 26.5 gram acidification pseudo-boehmites in slurries (salic 15 weight %, the pH value is 2.0, used acid is hydrochloric acid; Catalyst Shandong branch company of China Petrochemical Industry product) and the mixture of 37.5 gram SPAs (concentration is 85 weight %, Beijing Chemical Plant produce), wherein contain phosphorous oxide 35.9 weight %; Aluminium oxide 6.25 weight %; The pH value is 2.0, and particle diameter is distributed as 50～84nm, and average grain diameter is 68nm.Weight in phosphorus pentoxide and alundum (Al; The phosphorus al compsn weight of introducing accounts for 18 weight % of molecular sieve weight; Stirred 30 minutes, and added 22.5 gram glycerine solution (the glycerine weight percentage is 6 weight %), glycerine solution addition is 15 weight % of molecular sieve weight; Stir and obtained catalyst coat in 10 minutes and prepare mix slurry, wherein molecular sieve content is 15 weight %.Catalyst coat is prepared all ducts that mix slurry is full of honeycomb substrate, blow off the carrier outer surface with compressed air, 120 ℃ of down oven dry 3 hours, 650 ℃ of following roastings 1 hour obtain the honeycomb substrate catalyst.
The method purging honeycomb catalyst of describing according to instance 1 carries out the deflation experiment, and weighing result is listed in the table 1.
Instance 5
With 160 gram SAPO-11 molecular sieve powder (d90=14 micron, technical grade, catalyst Shandong branch company of China Petrochemical Industry product), mix with 217.4 gram deionized waters, wet ball grinding becomes slurries, particle diameter d90=5 micron; To the mixture that wherein adds 5 gram boehmites (in butt), 35 gram decationizing water and 20.5 gram SPAs (concentration 85 weight %, the Beijing Chemical Plant produces), wherein contain phosphorous oxide 20.8 weight % then; Aluminium oxide 8.3 weight %; The pH value is 2.5, and particle diameter is 24～40nm, and average grain diameter is 30nm; In phosphorus pentoxide and alundum (Al, the addition of phosphorus aluminium glue mixture is 11 weight % of molecular sieve weight; Stirred 30 minutes, and added poly-vinyl alcohol solution 19.2 grams (the polyvinyl alcohol percetage by weight is 1 weight %), addition is 12 weight % of molecular sieve weight, stirs and obtains the coating slurries in 20 minutes, and molecular sieve content is 35 weight % in the slurries.Gained coating slurries are full of all ducts of honeycomb substrate, blow off the carrier outer surface, 120 ℃ of oven dry 2 hours down, 650 ℃ of following roastings 1.5 hours with compressed air.
The method purging honeycomb catalyst of describing according to instance 1 carries out the deflation experiment, and weighing result is listed in the table 1.
Embodiment 6
With 180 gram HZSM-5 type molecular sieve powder (silica alumina ratio is 60 for d90=14 micron, catalyst Shandong branch company of China Petrochemical Industry product), mix with 87.6 gram distilled water, wet ball grinding becomes slurries, sieve particle diameter d 90=5 micron in the slurries; Add polyethylene glycol and polyacrylic acid mixed solution 32.4 grams (polyethylene glycol and polyacrylic acid percetage by weight are divided into 3 weight % and 5 weight %), addition is 18 weight % of molecular sieve weight, stirs 30 minutes; In slurries, add 60 gram phosphorus aluminium glues then (with embodiment 3; Wherein contain phosphorous oxide 12 weight %, aluminium oxide 3 weight %, the pH value is 1.6, particle diameter is 13～35nm, average grain diameter is 24nm), phosphorus aluminium glue addition is 5 weight % of molecular sieve weight, stirs to obtain catalyst coat in 60 minutes and prepare mix slurry.Resulting catalyst coat is prepared all ducts that mix slurry is full of honeycomb substrate, blow off the carrier outer surface, 120 ℃ of down oven dry 1.5 hours, 650 ℃ of following roastings 2 hours with compressed air.
The method purging honeycomb catalyst of describing according to instance 1 carries out the deflation experiment, and weighing result is listed in the table 1.
Embodiment 7～12
Embodiment 7～12 explanations regular catalyst provided by the invention is used for the effect of steam cracking.
The ordered structure catalyst that embodiment 1～6 is provided is seated in the tubular reactor respectively; Be to contact in reactor with ordered structure catalyst after the olefin containing gasoline of 37.6 weight % is preheating to 250 ℃ with olefin(e) centent then; Inject the water vapour of 250 ℃ of preheatings simultaneously, the weight (hourly) space velocity (WHSV) that keeps feedstock oil to inject is 20 hours
-1, water/oily feed weight ratio is 0.05, reaction temperature is 620 ℃, and pressure 0.05MPa (gauge pressure), the products therefrom sampling is analyzed in continuous feed 2.0 hours.Reaction result is seen table 2.
Comparative Examples 1
The active component of 100 gram HZSM-5 molecular sieves (with the HZSM-5 molecular sieve of embodiment 3), boehmites, iron oxide, lanthana and cerium oxide joined (wherein molecular sieve content is 75% in the deionized water; Matrix content 20%; Metal oxide content 5%), regulating pH is 4, processes the slurry that solid content is 35 weight %; Wet ball grinding is to particle diameter d90=5 micron then; Afterwards 1 gram poly-vinyl alcohol solution (regulate pH=4 with formic acid in advance, addition is equivalent to molecular sieve butt weight 1.0 weight %) is joined in the slurry, the method that the back that stirs is described according to instance 1 is prepared into honeycomb structured catalyst configurations; And carry out deflation according to the method purging honeycomb catalyst that instance 1 is described and test, the result lists in the table 1.
Comparative Examples 2
Restrain (in butt 108; HY type molecular sieve powder (d90=14 micron down together); Technical grade, catalyst Shandong branch company of China Petrochemical Industry product) mix with 200 gram deionized waters, in slurries, add 128 gram phosphorus aluminium glues (with boehmite and the making beating of decationizing water; Stir adding SPA down, make after the temperature reaction.Wherein contain phosphorous oxide 18 weight %, aluminium oxide 3 weight %, the pH value is 1.2; Granularity is 27～55nm; Average grain diameter is 32nm), be 25 weight % of molecular sieve weight in the addition of phosphorous oxide, aluminium oxide phosphorus aluminium glue, dry down after 30 minutes with the homogenizer stirring in 120 ℃.
Dried compound particles is levigate with agate mortar; Add 200 gram deionized waters; To particle diameter d90=5 micron, add polyglycol solution 3.24 grams (percetage by weight of polyethylene glycol is 2 weight %) with wet ball grinding afterwards, the addition of this solution is 3 weight % of molecular sieve weight; Stir and obtained catalyst coat in 20 minutes and prepare mix slurry (coating slurries), molecular sieve content is 30 weight % in the slurries.
Prepared catalyst coat is prepared mix slurry be full of cordierite honeycomb carrier (31 hole/square centimeters; Non-metal chemical mechinery works, Yixing, Jiangsu honeycomb pottery subsidiary factory product;) all ducts, blow off the carrier outer surface with compressed air, 120 ℃ of down oven dry 2 hours; 650 ℃ of following roastings 1 hour obtain having the honeycomb structured catalyst configurations of molecular sieve catalyst coating.
Using flow velocity is the duct 5 minutes that the honeycomb structured catalyst configurations that obtains is swept in 10 meter per second normal temperature (25 ℃) air wind, weighs, and obtains the weight that normal temperature air purges the back honeycomb structured catalyst configurations; Using flow velocity then is 10 meter per seconds, and temperature is to weigh in the duct of the honeycomb structured catalyst configurations that obtains of 400 ℃ warm air blowoff in 5 minutes, obtains the weight of honeycomb structured catalyst configurations after the warm air blowoff.The weight of honeycomb structured catalyst configurations after the weight of honeycomb structured catalyst configurations and the warm air blowoff was listed in the table 1 after weight, the normal temperature air of honeycomb structured catalyst configurations purged behind the weight of the honeycomb substrate of uncoated catalyst coat (carrier bare weight), the coating supported catalyst.
Comparative Examples 3～4
According to the experimental technique of embodiment 7～12, the ordered structure catalyst for preparing with Comparative Examples 1 and 2 carries out the gasoline conversion reaction, and the result sees table 2.
Table 1
Visible by table 1, after the catalyst coat of the inventive method preparation was handled through harsh conditions, coating loss was less; Even can be zero; The fastness that coating is described is better, and the catalyst coat loss of existing method preparation is bigger, handles through low temperature and the deflation of high temperature gas; The loss in addition can reach 15.9 and 24.06 weight %, fastness is relatively poor.
Table 2
Visible by table 2, the catalyst of the inventive method preparation has higher olefin conversion and propene yield, and the propylene selectivity is higher.
Claims (14)
1. a honeycomb substrate method for preparing catalyst that comprises the combination of molecular sieve coating comprises the step that applies honeycomb substrate with the coating slurries; Wherein, Said coating slurries comprise molecular sieve, phosphorus al compsn and water, contain or do not contain dispersant, are benchmark with the weight of coating slurries; The content of molecular sieve is 3～60 weight % in the said coating slurries; The weight ratio of phosphorus al compsn and molecular sieve is 0.1～30: 100, and the weight ratio of dispersant and molecular sieve is 0～20: 100, and wherein the weight of phosphorus al compsn is with P
2O
5And Al
2O
3The gross weight meter, molecular sieve is in butt weight; Said dispersant is selected from has polyhydroxy in the molecule, in the compound of polyoxyethylene groups or polycarboxylic acids base one or more, and the particle diameter of said phosphorus al compsn is less than 100nm, and said sieve particle diameter d 90 is 1～10 micron.
2. according to the described method of claim 1, it is characterized in that said coating slurries are prepared by the method that may further comprise the steps:
(1) molecular sieve is mixed with water, grind, obtain sieve particle diameter d 90 and be 1～10 micron slurries;
(2) slurries that step (1) obtained, particle diameter all mix less than 100nm phosphorus al compsn and dispersant solution.
3. according to the described method of claim 2, it is characterized in that said slurries, phosphorus al compsn and the dispersant solution that step (1) is obtained of step (2) is mixed into: in the slurries that step (1) obtains, add the phosphorus al compsn, stir, add dispersant solution.
4. according to the described method of claim 3, it is characterized in that the time of said stirring is 15～120 minutes; Stirred 10～60 minutes after adding dispersant.
5. according to each described method of claim 1～4, it is characterized in that described sieve particle diameter d 90 is 4～8 microns.
6. according to each described method of claim 1～5, it is characterized in that described phosphorus al compsn is particle diameter can form the phosphorus aluminium glue less than 100nm less than 100nm phosphorus aluminium glue and/or particle diameter a presoma material.
7. according to each described method of claim 1～5, it is characterized in that the particle diameter of said phosphorus al compsn is 1～60nm, average grain diameter 5～30nm.
8. according to the described method of claim 2, it is characterized in that the concentration of dispersant is 1～10 weight % in the said dispersant solution;
9. according to the described method of claim 1, it is characterized in that the weight ratio of dispersant and molecular sieve is 0.05～18: 100; The weight ratio of phosphorus al compsn and molecular sieve is 0.3～25: 100.
10. according to the described method of claim 6, it is characterized in that the said presoma material that forms the phosphorus aluminium glue is can be by the mixture of the aluminium hydroxide of sour peptization or aluminium oxide and SPA; Wherein said can be in ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-aluminium oxide, δ-aluminium oxide, the θ-aluminium oxide one or more by the aluminium oxide of sour peptization: described can be in gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite, the boehmite one or more by the aluminium hydroxide of sour peptization.
11., it is characterized in that dispersant is selected from one or more in polyethylene glycol, glycerine, polyvinyl alcohol or the polyacrylic acid according to each described method of claim 1～9.
12. coating slurries; Comprising molecular sieve, phosphorus al compsn and water, contain or do not contain dispersant, is benchmark with the weight of slurries; The content of molecular sieve is 3～60 weight % in the said coating slurries; The weight ratio of phosphorus aluminium and molecular sieve is 0.1～30: 100, and the weight ratio of dispersant and molecular sieve is 0～20: 100, and said dispersant is selected from has polyhydroxy in the molecule, in the compound of polyoxyethylene groups or polycarboxylic acids base one or more; The particle diameter of said phosphorus al compsn is less than 100nm, and sieve particle diameter d 90 is 1～10 micron.
13., it is characterized in that described sieve particle diameter d 90 is 4～8 microns according to the described slurries of claim 12, the particle diameter of said phosphorus al compsn is 1～90nm, the weight ratio of dispersant and molecular sieve is 0.05～18: 100.
14. the preparation method of coating slurries, said coating slurries comprise molecular sieve, phosphorus al compsn and water, contain or do not contain dispersant, and said preparation method may further comprise the steps:
(1) molecular sieve is mixed with water, grind, obtain sieve particle diameter d 90 and be 1～10 micron slurries;
(2) slurries that step (1) obtained, particle diameter mix less than phosphorus al compsn and the dispersant solution of 100nm.
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