CN102451741A - Preparation method of honeycomb substrate catalyst with molecular sieve composition coating - Google Patents
Preparation method of honeycomb substrate catalyst with molecular sieve composition coating Download PDFInfo
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Abstract
A preparation method of a honeycomb substrate catalyst with a molecular sieve composition coating comprises the step of coating a honeycomb substrate with coating slurry; the coating slurry comprises a molecular sieve, an alumina component, and water with or without a dispersant; on a basis of the weight of the coating slurry, the molecular sieve content in the coating slurry is 3-60 wt%; the weight ratio of the alumina component and the molecular sieve is 0.1-30:100; and the weight ratio of the dispersant and the molecular sieve is 0-20:100, wherein the alumina component is on a basis of Al2O3, and the molecular sieve is on a dry basis; the dispersant is selected from one or more than one of compounds with polyhydroxy, polyoxyethylene groups, or poly-carboxylic groups in molecules; the alumina component has a particle diameter of less than 100 nm; the molecular sieve has a particle diameter d 90 of 1-10 microns. The honeycomb substrate catalyst with the molecular sieve composition prepared by the invention has a firm coating; the prepared gasoline conversion catalyst has a high alkene conversion rate and a high propylene yield.
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 that gasoline transforms that is used for.
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; Synthetic reaction finishes, on the duct inwall in the carrier " growth " go out molecular sieve layer, but the catalyst quality instability of this method preparation; Duplicate difficulty, be difficult for industry and amplify.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 catalyst activity component coating fastness is relatively poor, and the use floating coat is easy to come off.
Summary of the invention
The technical problem that the present invention will solve is to transform the relatively poor problem of honeycomb substrate catalyst fastness to existing gasoline; Provide a kind of gasoline that is used for to transform the honeycomb substrate method for preparing catalyst that comprises the combination of molecular sieve coating, 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, the preparation of said coating slurries 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 the alumina component of 100nm, add or do not add dispersant;
Weight with the coating slurries is benchmark; The content of molecular sieve is 3～60 weight % in the said coating slurries; The weight ratio of alumina component and molecular sieve is 0.1～30: 100; When containing dispersant in the said coating slurries, the weight ratio of dispersant and molecular sieve is 0～20: 100, and wherein the weight of alumina component is with Al
2O
3The weight meter, molecular sieve is in butt; Said dispersant is selected from has polyhydroxy in the molecule, in the compound of polyoxyethylene groups or polycarboxylic acids base one or more.
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, alumina component 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, alumina component is (with Al
2O
3Meter) weight ratio with molecular sieve (in butt) is 0.1～30: 100; 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 or polyoxyethylene groups are arranged in the molecule; Said sieve particle diameter d 90 is 1～10 micron, and the particle diameter of alumina component is no more than 100nm.
Alumina component particle diameter Determination of distribution method adopts light correlation spectroscopy (PCS), sees ASTME2490, and the measuring method of sieve particle diameter adopts the laser particle analyzer method, referring to ASTMD4464-00 (2005).
The present invention also provides the preparation method of said 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 that step (1) is obtained and particle diameter mix less than the 100nm alumina component, add or do not add dispersant solution, obtain the coating slurries.
The honeycomb substrate method for preparing catalyst that comprises the combination of molecular sieve coating provided by the invention earlier is prepared into molecular sieve and a kind ofly contains sieve particle, alumina component and water, contains or non-dispersant coating slurries, 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 honeycomb substrate catalyst of fastness; Prepared cracking gasoline transforms the honeycomb substrate catalyst, good catalyst activity, and selectivity is good; Olefin conversion is high, and productivity of propylene is high.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; Preferred described coating slurries comprise dispersant; In the said coating slurries that comprise molecular sieve, alumina component, dispersant solution and water; Gross weight with the coating slurries is a benchmark, is 3～60 weight % in the butt molecular sieve content, is preferably 5～55 weight %; Alumina component is (with Al
2O
3Meter) is 0.1～30: 100 with the weight ratio of molecular sieve (in butt), is preferably 0.3～25: 100, more preferably 5～25: 100; The weight ratio of dispersant and molecular sieve is preferably 0.01～20: 100, more 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 alumina component is particle diameter less than the aluminium oxide of 100nm and/or can forms the presoma material of aluminium oxide; The particle diameter of said alumina component is preferably 1～90nm; More preferably 1～60nm, average grain diameter (diameter) is preferably 2～70nm, more preferably 5～45nm.The solid content of prepared slurries is preferably 3～60 weight %.
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, alumina component and dispersant solution mix; Wherein the content of dispersant is 1～10 weight % in the dispersant solution; Said alumina component is aluminium oxide and/or the presoma material that can form aluminium oxide; The particle diameter of aluminium oxide and the presoma material that can form aluminium oxide is all less than 100nm; Be preferably 1～90nm; 1～60nm more preferably, average grain diameter (diameter) is preferably 2～70nm, more preferably 5～45nm.
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 the employing wet ball grinding, and it is 1～10 micron that said grinding makes the d90 of sieve particle diameter in the slurries.Have good fastness in order to make prepared gasoline transform the honeycomb substrate catalyst, and have better alkene activity of conversion and propylene selectivity, the particle diameter d90 of described sieve particle is preferably 4～8 microns; The weight ratio of described alumina component and molecular sieve is preferably 0.3～25: 100.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, diameter accounts for 90% of sieve particle cumulative volume in the slurries less than the sieve particle volume of this value (d90) in the slurries.
Can molecular sieve pulp, alumina component (aluminium oxide and/or can form the presoma material of aluminium oxide) 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 aluminium oxide and/or can form the presoma material of aluminium oxide; Stir; Preferred mixing time was at least 5 minutes, and preferred mixing time is 15～120 minutes, adds dispersant solution then and stirs; Preferably, stirred 10～60 minutes behind the adding dispersant solution.Can also comprise clay in the said coating slurries, when comprising clay in the described coating slurries, said clay preferably added before dispersant, more preferably before alumina component, added.Said alumina component particle diameter is no more than 100 nanometers, is preferably 1～60 nanometer, preferred 5～45 nanometers of average grain diameter.The presoma material that can form aluminium oxide can be selected from aluminium colloidal sol, one or more in the boehmite.The d90 of said clay slurry medium clay soil is 1～10 micron, is preferably 4～8 microns, and said clay can be selected from kaolin, halloysite, imvite, diatomite, tired in the soil one or more, the preferred kaolin of taking off.
In the step (2), the adding weight of preferred 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, said dispersant is one or more in polyethylene glycol, glycerine, polyvinyl alcohol or the polyacrylic acid for example.
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 silicoaluminophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO) that silicate (like metal silicate metallosilicate, titan silicate titanosilicate) with Different Silicon aluminum ratio, metal aluminate metalloaluminates (like germanium aluminate germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphate metalloaluminophosphates, metal combines, silicoaluminophosphate 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; Described with coating slurries coating honeycomb substrate, can comprise the coating slurries are contacted with honeycomb substrate according to existing method; 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.The wherein said method that blows off the carrier outer surface with compressed air; Can be according to existing method; CN1191127C disclosed method for example, described drying can adopt the mode of oven dry, for example 100～120 ℃ of oven dry 2～5 hours down; Preferred 600～700 ℃ of the temperature of said roasting, preferred 1～3 hour of roasting time.Obtain containing the honeycomb substrate catalyst of combination of molecular sieve coating after the roasting.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 catalyst that contains the combination of molecular sieve coating provided by the invention, coating levels are 0.1～40 weight %, and honeycomb substrate content is 60～99.9 weight %.The said content of the honeycomb substrate catalyst floating coat of combination of molecular sieve coating that comprises is preferably 0.5～35 weight %.
The honeycomb substrate method for preparing catalyst that comprises the combination of molecular sieve coating provided by the invention; Prepared catalyst; Coating is firm; Be difficult for chapping and coming off, be applicable to that preparation comprises the honeycomb substrate catalyst of macromolecule sieve content coating, for example is used for the gasoline catalyzing cracking and produces propylene honeycomb substrate Preparation of catalysts.
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.
Embodiment 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) mix with 120.5 gram deionized waters, wet ball grinding becomes molecular sieve pulp, sieve particle diameter d 90=5 micron; (the pH value is 2.2 for salic 21 weight %, the production of catalyst Shandong branch company of China Petrochemical Industry in slurries, to add 128 gram aluminium colloidal sols; Particle diameter is 15～45nm, and average grain diameter is 30nm), be 25 weight % of molecular sieve weight in the addition of aluminium oxide aluminium colloidal sol; Stirred 10 minutes; Add polyglycol solution 3.24 grams (content of polyethylene glycol is 2 weight %), the addition of this solution is 3 weight % of molecular sieve weight, stirs to obtain catalyst coat in 20 minutes and prepare mix slurry (coating slurries).Molecular sieve content is 30 weight % in the slurries, prepares mix slurry with prepared catalyst coat and applies 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; Blow off surperficial unnecessary carrier 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 after the weight of honeycomb structured catalyst configurations and the warm air blowoff after weight, the normal temperature air of honeycomb structured catalyst configurations purge behind the weight of the honeycomb substrate of uncoated catalyst coat (carrier bare weight), the coating supported catalyst, the result lists in the table 1.
Embodiment 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 204 gram deionized waters, wet ball grinding becomes slurries, sieve particle diameter d 90=8 micron in the slurries; Adding 144 gram aluminium colloidal sols in slurries (salic 10 weight %, Zhejiang Province Yuda Chemical Co., Ltd's product, particle diameter are 5～15 nanometers, and average grain diameter is 10nm, and pH=4), the aluminium oxide addition is 12 weight % of molecular sieve weight, stirs 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 (with embodiment 1 said honeycomb substrate), 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 embodiment 1 carries out the deflation experiment, and the result lists in the table 1.
Embodiment 3
With 180 gram HZSM-5 type molecular sieve powder (d90=14 micron, silica alumina ratio are 60, catalyst Shandong branch company of China Petrochemical Industry product), mix with 122.6 gram distilled water, wet ball grinding becomes slurries, sieve particle diameter d 90=5 micron in the slurries; In slurries, add 25 gram aluminium colloidal sols (particle diameter is 35～55 nanometers for salic 36 weight %, catalyst Shandong branch company of China Petrochemical Industry product, and average grain diameter is 42nm), the aluminium oxide addition is 5 weight % of molecular sieve weight, stirs 60 minutes; (polyethyleneglycol content is 3 weight % to add polyethylene glycol and polyacrylic acid mixed solution 32.4 grams; Polyacrylic acid content is 5 weight %); The solution addition is 18 weight % of molecular sieve weight; Stir and obtained catalyst coat in 30 minutes and prepare mix slurry, molecular sieve content is 50 weight % in the slurries.Resulting catalyst coat is prepared all ducts that mix slurry is full of honeycomb substrate (with embodiment 1 said 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 embodiment 1 carries out the deflation experiment, and the result lists in the table 1.
Embodiment 4
With 100 gram HY 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 557.5 grams, wet ball grinding becomes slurries, the particle diameter d90=5 micron of molecular sieve in the slurries; (particle diameter is 1～26 nanometer for salic 10 weight %, catalyst Shandong branch company of China Petrochemical Industry product in slurries, to add 270 gram acidification pseudo-boehmites; Average grain diameter is 5nm; The pH value is 1.9), the alumina amount that boehmite is introduced accounts for 18 weight % of molecular sieve weight, stirs 30 minutes; Add 22.5 gram glycerine solution (the glycerine weight percentage is 6 weight %); Glycerine solution addition is 15 weight % of molecular sieve weight, stirs to obtain catalyst coat in 10 minutes and prepare mix slurry, and wherein molecular sieve content is 15 weight %.Catalyst coat is prepared all ducts that mix slurry is full of honeycomb substrate (with embodiment 1 said 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 embodiment 1 carries out the deflation experiment, and weighing result is listed in the table 1.
Embodiment 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 142 gram deionized waters, wet ball grinding becomes slurries, particle diameter d90=5 micron; (particle diameter is 15～38nm for salic 20 weight %, catalyst Shandong branch company of China Petrochemical Industry product to wherein adding 40 gram Ludox then; Average grain diameter is 26nm) and 96 gram acidification pseudo-boehmites (salic 10 weight %, catalyst Shandong branch company of China Petrochemical Industry product is with embodiment 4); The aluminium oxide addition 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; Stir and obtained catalyst coat in 20 minutes and prepare mix slurry, its molecular sieve content is 35 weight %.The gained catalyst coat is prepared all ducts that mix slurry is full of honeycomb substrate (with embodiment 1 said honeycomb substrate), blow off the carrier outer surface, 120 ℃ of down oven dry 2 hours, 650 ℃ of following roastings 1.5 hours with compressed air.
The method purging honeycomb catalyst of describing according to embodiment 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 (d90=14 micron, silica alumina ratio are 60, catalyst Shandong branch company of China Petrochemical Industry product), mix with 122.6 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; (granularity is 35～85 nanometers for salic 36 weight %, catalyst Shandong branch company of China Petrochemical Industry product to add 25 gram aluminium colloidal sols then; Average grain diameter is 60nm); The aluminium oxide addition is 5 weight % of molecular sieve weight, stirs 60 minutes, obtains catalyst coat and prepares mix slurry.Molecular sieve is 50 weight % in the slurries.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 embodiment 1 carries out the deflation experiment, and weighing result is listed in the table 1.
Comparative Examples 1
The active component of 100 gram HZSM-5 molecular sieves (with 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 back that stirs is prepared into honeycomb structured catalyst configurations according to the method that embodiment 1 describes; And carry out deflation according to the method purging honeycomb catalyst that embodiment 1 describes and test, the result lists in the table 1.
Comparative Examples 2
108 gram (in butt) HY type molecular sieve powder (d90=14 micron, technical grade, catalyst Shandong branch company of China Petrochemical Industry product) are mixed with 200 gram deionized waters; (the pH value is 2.2 for salic 21 weight %, the production of catalyst Shandong branch company of China Petrochemical Industry in slurries, to add 128 gram aluminium colloidal sols; Granularity is 15～45nm; Average grain diameter is 30nm), be 25 weight % of molecular sieve weight in the addition of aluminium oxide aluminium colloidal sol, 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 honeycomb substrate (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.
Table 1
Visible by table 1, after the catalyst coat of the inventive method preparation was handled through harsh conditions, coating loss was less; And the catalyst coat loss of existing method preparation is bigger, handles through low temperature and high-temperature gas deflation, loses even can reach 15.9 and 20.8 weight %, shows that its coating fastness is poor than the catalyst that the inventive method obtains.
Comparative Examples 3
With 160 gram HY type molecular sieve powder (d90=14 micron, catalyst Shandong branch company of China Petrochemical Industry product), mix making beating with 320 gram deionized waters, preparation solid content 50 weight % molecular sieve pulps; In 110 ml deionized water, add 76 gram boehmites (Shandong Aluminium Industrial Corp's product, alumina content 32 weight %); 90 ℃ are stirred to evenly, and processing solid content is the boehmite slurries of 15 weight %; Get the half the of above-mentioned boehmite slurries; Using the salt acid for adjusting pH value of mass concentration 20% is 2～3; Stir and added above-mentioned molecular sieve pulp in 30 minutes, stir and added remaining second half boehmite slurries in 30 minutes again, stirred 30 minutes; The aluminium colloidal sol (production of catalyst Shandong branch company of China Petrochemical Industry, the Al that add 0.1 times of HY quality
2O
3Content 22 weight %), stirred 40 minutes, obtain Preparation of Catalyst coating slurries.Apply honeycomb substrate (with embodiment 1 said honeycomb substrate) with said slurries then, dried 2 hours down for 120 ℃, 650 ℃ of following roastings obtained having the honeycomb structured catalyst configurations of molecular sieve catalyst coating in 1 hour.
Embodiment 7
With the catalyst use olefin(e) centent of the catalyst of Comparative Examples 2,3 methods preparations and the preparation of embodiment 1 method is that the gasoline of 41 weight % is estimated appreciation condition: reaction temperature is 620 ℃, and weight (hourly) space velocity (WHSV) is 20h
-1, introduce the dilution water steam, water oil feed weight ratio is 0.05, and feeding temperature is 250 ℃, and pressure is 0.05MPa (gauge pressure).Its olefin conversion of catalyst of embodiment 1 method preparation is 52.05 weight %, propene yield 26.35 weight %; The catalyst of Comparative Examples 2 methods preparation, its olefin conversion is respectively 34.55 weight % propene yields and is respectively the catalyst for preparing with 8.07 weight % Comparative Examples, 2 methods.The olefin conversion of Comparative Examples 3 catalyst is 48.38 weight %, and propene yield is merely 20.80 weight %.It is thus clear that the catalyst of the inventive method preparation has higher alkene and transforms aluminium and propene yield.
Embodiment 8
Method according to embodiment 1 prepares catalyst, and the weight ratio of different is aluminium oxide and molecular sieve is 1: 100, its low temperature deflation loss 0, high temperature deflation loss 0.
Embodiment 9～14
Embodiment 2～6 is seated in the tubular reactor with the ordered structure catalyst of Comparative Examples 1 preparation; 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, and water/oily feed weight ratio is 0.05, is that 620 ℃, pressure are 0.05MPa (gauge pressure) in reaction temperature; The products therefrom sampling is analyzed in continuous feed 2.0 hours.Reaction result is seen table 2.
Table 2
Visible by table 2, catalyst olefin conversion provided by the invention is higher, and propene yield and propylene selectivity are higher.
Claims (11)
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, the preparation of said coating slurries 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 the 100nm alumina component, add or do not add dispersant;
Weight with the coating slurries is benchmark, and the content of molecular sieve is 3～60 weight % in the said coating slurries, and the weight ratio of alumina component and molecular sieve is 0.1～30: 100, and the weight ratio of dispersant and molecular sieve is 0～20: 100, and wherein alumina component is with Al
2O
3The weight meter, molecular sieve is in butt; Said dispersant is selected from has polyhydroxy in the molecule, in the compound of polyoxyethylene groups or polycarboxylic acids base one or more.
2. according to the described method of claim 1; It is characterized in that; Add dispersant in the step (2), said slurries, alumina component and the dispersant solution that step (1) is obtained is mixed into: in the slurries that step (1) obtains, add the presoma material that aluminium oxide maybe can form aluminium oxide, stir; Add dispersant solution, the weight ratio of dispersant and molecular sieve is 0.01～20: 100.
3. according to the described method of claim 2, it is characterized in that the time of said stirring is 10～120 minutes.
4. 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; The weight ratio of dispersant solution and molecular sieve is 0.01～20: 100.
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 the particle diameter of said alumina component is 1～60nm, average grain diameter 5～45nm.
7. according to each described method of claim 1～5, it is characterized in that the weight ratio of alumina component and molecular sieve is 0.3～25: 100.
8. according to the described method of claim 1, it is characterized in that described alumina component is aluminium colloidal sol and/or boehmite.
9. according to each described method of claim 1～8, it is characterized in that dispersant is selected from one or more in polyethylene glycol, glycerine, polyvinyl alcohol or the polyacrylic acid.
10. coating slurries comprise molecular sieve, alumina component and water, contain or do not contain dispersant; Wherein, Weight with slurries is benchmark, and the content of molecular sieve is 3～60 weight % in the said coating slurries, and the weight ratio of alumina component and molecular sieve is 0.1～30: 100; The weight ratio of dispersant and molecular sieve is 0～20: 100; 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 alumina component is less than 100nm, and sieve particle diameter d 90 is 1～10 micron.
11. the preparation method of the said coating slurries of claim 10 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 and the particle diameter that step (1) are obtained mix less than the 100nm alumina component, add or do not add dispersant.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888841A (en) * | 2015-05-26 | 2015-09-09 | 华东理工大学 | Preparation method of monolithic catalyst with molecular sieve type coating |
| CN105435833A (en) * | 2014-08-12 | 2016-03-30 | 凯龙蓝烽新材料科技有限公司 | Selective catalytic reduction (SCR) catalyst preparation method |
| CN107297218A (en) * | 2017-06-27 | 2017-10-27 | 中国第汽车股份有限公司 | Molecular sieve cordierite honeycomb carrier method for preparing catalyst |
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| US4988653A (en) * | 1988-12-30 | 1991-01-29 | Mobil Oil Corporation | Elutriable multi component cracking catalyst mixture and a process for catalytic cracking of heavy hydrocarbon feed to lighter products |
| CN1986742A (en) * | 2005-12-21 | 2007-06-27 | 中国石油化工股份有限公司 | Method of lowering olefine content in gasoline |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4988653A (en) * | 1988-12-30 | 1991-01-29 | Mobil Oil Corporation | Elutriable multi component cracking catalyst mixture and a process for catalytic cracking of heavy hydrocarbon feed to lighter products |
| CN1986742A (en) * | 2005-12-21 | 2007-06-27 | 中国石油化工股份有限公司 | Method of lowering olefine content in gasoline |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435833A (en) * | 2014-08-12 | 2016-03-30 | 凯龙蓝烽新材料科技有限公司 | Selective catalytic reduction (SCR) catalyst preparation method |
| CN104888841A (en) * | 2015-05-26 | 2015-09-09 | 华东理工大学 | Preparation method of monolithic catalyst with molecular sieve type coating |
| CN107297218A (en) * | 2017-06-27 | 2017-10-27 | 中国第汽车股份有限公司 | Molecular sieve cordierite honeycomb carrier method for preparing catalyst |
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| CN102451741B (en) | 2014-03-12 |
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