CN102451738A - Regular structure catalyst for preparation of propylene by steam cracking, and application thereof - Google Patents
Regular structure catalyst for preparation of propylene by steam cracking, and application thereof Download PDFInfo
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Abstract
The invention relates to a regular structure catalyst for preparation of propylene by steam cracking, and an application thereof. The catalyst comprises, by weight, 60-99.9% of a honeycomb carrier, and 0.1-40% of an active coating, wherein the active coating comprises a molecular sieve and a silicon oxide matrix. The preparation method for the regular structure catalyst comprises: (1) preparing a molecular sieve slurry with the particle diameter d90 of 1-10 mum; (2) mixing the slurry with the silicon oxide component with the particle diameter less than 100 nm, wherein a dispersing agent is added or is not added to obtain a coating slurry; and (3) coating the honeycomb carrier by the coating slurry. The molecular sieve composition-containing regular structure catalyst prepared by the method of the present invention has the following advantages that: the coating is solid, and does not easily shed; the service life is long; the catalyst can be used for catalytic cracking of the FCC gasoline; the catalyst has high activity; the propylene selectivity is high; the coke yield is low.
Description
Technical field
The present invention relates to a kind of ordered structure catalyst of hydrocarbon ils steam cracking system propylene.
Background technology
The honeycomb substrate catalyst is applied aspect Industrial Catalysis in recent years.Novel ordered structure catalyst generally includes regular carrier and active component coating.In the hydrocarbon oil conversion reaction that utilizes ordered structure catalyst,, use molecular sieve in its active component coating usually in order to reduce reaction temperature.For example CN100448947C discloses a kind of method that reduces olefin(e) centent in the gasoline, and olefin containing gasoline is contacted with ordered structure catalyst with oil, in reducing gasoline, in the olefin(e) centent, generates propylene, ethene.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 to prepare the combination of molecular sieve particle earlier, again the composition grain ball milling is become slurries and adds surfactant, or use the surfactant solution modified support earlier, applies combination of molecular sieve then to the honeycomb substrate duct.But this catalyst coat fastness is relatively poor, and in use coating is easy to come off, and when being used for the gasoline conversion, olefin conversion is not high, and propylene and selectivity of ethylene are relatively poor.
CN1903808A discloses a kind of method by olefine containing gasoline catalytic cracking system propylene; Comprise with described olefin containing gasoline in the presence of water vapour with catalyst 450～650 ℃ of haptoreactions; Make the olefin cracking in the gasoline generate propylene, wherein said catalyst comprises the aluminium oxide of 2～60 weight % and the modified ZSM-5 zeolite of 40～98 weight %.Yet this method does not relate to the fastness that improves catalyst coat, and prepared catalyst coat fastness is relatively poor, and propene yield is not high.
Summary of the invention
The technical problem that the present invention will solve is the problem that is used for the ordered structure catalyst coating fastness difference of steam cracking producing light olefins to existing, and a kind of ordered structure catalyst that comprises the combination of molecular sieve coating that is used for the steam cracking producing light olefins is provided.The other technical problem that the present invention will solve provides said Application of Catalyst method.
The present invention provides a kind of ordered structure catalyst that is used for steam cracking system propylene hydrocarbon; Said catalyst is made up of the honeycomb substrate of 60～99.9 weight % and the active coating of 0.1～40 weight %; Described active coating comprises molecular sieve and silicon oxide substrate, and said ordered structure catalyst preparation method comprises:
(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, particle diameter mix less than 100nm silica component, add or do not add dispersant, obtain the coating slurries; Wherein said silica component to be particle diameter can form silica less than silica and/or the particle diameter of 100nm less than 100nm presoma material; The content of molecular sieve is 3～60 weight % in the said coating slurries, and the silica component is (with SiO
2Meter) weight ratio with molecular sieve (in butt) 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;
(3) the coating slurries that obtain with step (2) apply honeycomb substrate.
Silica component particle diameter Determination of distribution method according to the invention can adopt light correlation spectroscopy (PCS), and referring to ASTM E2490, the measuring method of sieve particle diameter adopts the laser particle analyzer method, referring to ASTM D4464-00 (2005).
The present invention also provides a kind of method of gasoline vapor catalytic cracking for producing propylene using, comprises that steam makes gasoline and ordered structure catalyst provided by the invention 350～900 ℃ of haptoreactions under existing.
Honeycomb substrate catalyst provided by the invention; The combination of molecular sieve coating is firm; Difficult drop-off in the use, good catalyst activity is used for the conversion of FCC gasoline and has higher cracking of olefins activity and yield of light olefins; Be the yield and the propylene selectivity that can also improve propylene unexpectedly, have lower coke yield.The method of propylene is produced in gasoline vapor cracking provided by the invention, has higher alkene and transforms aluminium and propene yield.For example; The coating levels of existing method preparation is the catalyst of 40 weight %, and after the harsh conditions deflation, its coating loss is 15.9 weight %; And the coating levels of the present invention preparation to be the catalyst of 40 weight % handle at similarity condition, coating loss is 0; With olefin(e) centent is that the olefin containing gasoline of 37.6 weight % is a raw material, is 20 hours-1 in weight (hourly) space velocity (WHSV), and water/oily feed weight ratio is 0.05; Reaction temperature is 620 ℃ and reacts; Its olefin conversion of the catalyst that existing method obtains is 58.4 weight %, and propene yield is 18.77 weight %, and the propylene selectivity is 32.09 weight %; And its alkene of catalyst provided by the invention reach 72.5 weight %; The propylene selectivity can reach 61.26 weight %, and coke yield is lower, has being selected from property of coke preferably.
The specific embodiment
The ordered structure catalyst of steam cracking system propylene provided by the invention; Its preparation process is mixed molecular sieve in (1) with water; Grind then and obtain molecular sieve pulp; 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; In order to make described catalyst have higher alkene activity of conversion and selectivity of light olefin and to have fastness preferably, the d90 of described sieve particle diameter is preferably 4～8 microns; 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 sieve particle volume of this value (d90) in the slurries.
The preferred dispersant that adds in the step (2), the weight ratio of dispersant and molecular sieve is 0.01～20: 100.Can molecular sieve pulp, silica component (silica and/or can form the presoma material of silica) and dispersant solution be mixed through any existing method; Preferable methods is: in the molecular sieve pulp that step (1) obtains, add silica and/or can form the presoma material of silica; Stir; Preferred mixing time was at least 5 minutes; Preferred mixing time is 15～120 minutes, adds dispersant solution then and stirs, the preferred stirring 10～60 minutes behind the adding dispersant solution.Wherein the content of dispersant is 1～10 weight % in the dispersant solution.Said silica component is particle diameter less than the silica of 100nm and/or can forms the presoma material of silica; Preferably, the particle diameter of said silica component is 1～60nm, and average grain diameter (diameter) is 5～30nm; The particle diameter of silica and the presoma material that can form silica is preferably 1～60nm, more preferably 5～30nm all less than 100nm.The presoma material that can form silica can be selected from Ludox, one or more in the waterglass.Particle diameter less than the silica of 100nm for example particle diameter less than the nanometer hydrated silica of 100nm.
In the step (2), the addition of preferred described dispersant solution is 0.01～20 weight % of molecular sieve butt weight, and more preferably addition is 0.05～18 weight % of molecular sieve butt weight; Wherein the percetage by weight 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 be 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.
The coating slurries that step (2) obtains comprise molecular sieve, silica component, dispersant solution and water; The consumption of each component makes in the slurries that obtain; Gross weight with the coating slurries is a benchmark, is 3～60 weight % in the butt molecular sieve content, is preferably 5～55 weight %; The silica component is (with SiO
2Meter) 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 0.01～20: 100, is preferably 0.05～18: 100.The solid content of said coating slurries is preferably 3～60 weight %.
Molecular sieve according to the invention 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, alumino-silicate silicoaluminophosphates (SAPO), the gallium germanate (gallogermanates), is preferably the SAPO-11 molecular sieve.Described molecular sieve is preferably Y zeolite and/or ZSM-5 zeolite, and described Y zeolite is a Hydrogen or through rare earth modified zeolite.Described ZSM-5 zeolite is one or more in HZSM-5, phosphorus and transition metal modified ZSM-5 zeolite, the rare earth modified ZSM-5 zeolite, for example is ZRP zeolite and/or ZSP zeolite.
The ordered structure catalyst of steam cracking system propylene provided by the invention prepares in the process; The described coating honeycomb substrate of step (3) can carry out according to existing method, comprises the coating slurries are contacted with honeycomb substrate; 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.Wherein, the method that said use compressed air blows off the carrier outer surface is existing method, can be referring to the CN1191127C disclosed method; 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.Said honeycomb substrate can select for use commercially available composite oxides honeycomb substrate for example cordierite carrier also can select the honeycomb substrate of other material for use.
Can also contain clay in the ordered structure catalyst coating provided by the invention, when preparing the coating slurries in such cases, said clay adds in step (2), preferably before dispersant, adds, and more preferably before the silica component, adds.The d90 of said clay 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.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 %.
The ordered structure catalyst of steam cracking system propylene provided by the invention is a benchmark with the weight of catalyst, is made up of the honeycomb substrate of 60～99.9 weight % and the active coating of 0.1～40 weight %; Preferred active coating accounts for 2～35 weight %, and honeycomb substrate accounts for 65～98 weight %.Silicon oxide substrate is (with SiO in the active coating
2The weight meter) and the weight ratio of molecular sieve (in butt) be 0.1～30: 100; Preferably; Said active coating comprises 70～99.9% molecular sieve; 0.1～30 weight % silicon oxide substrates; Preferred said coating comprises the silicon oxide substrate of 0.3～25 weight % and the molecular sieve of 75～99.7 weight %, more preferably comprises the molecular sieve of 75～99 weight % and the silicon oxide substrate of 1～25 weight %.The coating layer thickness of said catalyst is 1nm～1mm, preferred 1～500 μ m.
The method of steam cracking system propylene provided by the invention is included in steam and makes gasoline and ordered structure catalyst provided by the invention 350～900 ℃ of preferred 400～650 ℃ of haptoreactions under existing.The weight ratio of steam and gasoline is 0.01～2: 1, preferred 0.1～2: 1; With the coating weight is benchmark, and the gasoline weight (hourly) space velocity (WHSV) is 10～350h
-1, preferred 10～100h
-1Pressure is not had specific (special) requirements, and normal pressure operation down gets final product, can be with reference to existing method.
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 68.76 gram deionized waters, wet ball grinding becomes molecular sieve pulp, sieve particle diameter d 90=5 micron; (modulus is 3.2 for silicon oxide-containing 15 weight %, the production of catalyst Shandong branch company of China Petrochemical Industry in slurries, to add 180 gram waterglass; Particle diameter is 1～5nm, and average grain diameter is 3nm.); Addition in silica waterglass 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 % in the solution), 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;); 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 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 252 gram deionized waters, wet ball grinding becomes slurries, sieve particle diameter d 90=8 micron in the slurries; (viscosity of silicon gel is 600cst (25 ℃) for silicon oxide-containing 15 weight %, catalyst Shandong branch company of China Petrochemical Industry product in slurries, to add 96 gram silicon gels; Ionic diameter is 5～15 nanometers; Average grain diameter is 12nm), the silica 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 (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 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 (silica alumina ratio is 60 for d90=14 micron, catalyst Shandong branch company of China Petrochemical Industry product), mix with 102.6 gram distilled water, wet ball grinding becomes slurries, sieve particle diameter d 90=5 micron in the slurries; In slurries, add 45 gram Ludox (silicon oxide-containing 20 weight %; Catalyst Shandong branch company of China Petrochemical Industry product, the particle diameter of Ludox is 12～35nm, average grain diameter is 20nm); The silica amount of being introduced by Ludox 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, 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 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 557.7 grams, wet ball grinding becomes slurries, the particle diameter d90=5 micron of molecular sieve in the slurries; Add 270 gram Ludox (silicon oxide-containing 10 weight % then; Catalyst Shandong branch company of China Petrochemical Industry, the silica sol particle diameter is 30～54nm, average grain diameter is 42nm); Account for 18 weight % of molecular sieve weight by the silica amount of Ludox introducing; 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 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 184 gram deionized waters, wet ball grinding becomes slurries, particle diameter d90=5 micron; (the silica sol particle diameter is 5～15nm for silicon oxide-containing 20 weight %, catalyst Shandong branch company of China Petrochemical Industry product to wherein adding 50 gram Ludox then; Average grain diameter is 10nm) and 44 gram silicon gels (viscosity of silicon gel is 600cst (25 ℃) for silicon oxide-containing 15 weight %, catalyst Shandong branch company of China Petrochemical Industry product; The particle diameter scope is 5～15 nanometers; Average grain diameter is 12nm), the silica addition is 11 weight % of molecular sieve weight, stirs 30 minutes; Add 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 to obtain catalyst coat in 20 minutes and prepare mix slurry, and molecular sieve content is 35 weight %.Resulting mixture is full of all ducts of honeycomb substrate, blows 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 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 (silica alumina ratio is 60 for d90=14 micron, catalyst Shandong branch company of China Petrochemical Industry product), mix with 102.6 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; Add 45 gram Ludox (silicon oxide-containing 20 weight % then; Catalyst Shandong branch company of China Petrochemical Industry product, the silica sol particle diameter is 12～35nm, average grain diameter is 20nm); The silica addition is 5 weight % of molecular sieve weight; Stirred 60 minutes, and obtained catalyst coat and prepare 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 particle diameter of silica component is 12～35nm, and average grain diameter is 20nm.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 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 in embodiment 1～6, provides is seated in the tubular reactor; 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, and reaction temperature is 620 ℃, and pressure is 0.05MPa (gauge pressure), and 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 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
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 200 gram deionized waters; (modulus is 3.2 for silicon oxide-containing 15 weight %, the production of catalyst Shandong branch company of China Petrochemical Industry in slurries, to add 180 gram waterglass; Particle diameter is 1～5nm, and average grain diameter is 3nm.), be 25 weight % of molecular sieve weight in the addition of silica waterglass, 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 (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
Comparative Examples 3～4 adopts the ordered structure catalyst that contains the molecular sieve coating of Comparative Examples 1～2 preparation, uses the experimental technique identical with embodiment 7～12, explains that catalyst provided by the invention is used for the effect of steam cracking reaction.Reaction result is seen table 2.
Table 1
Visible by table 1, after the catalyst process low temperature of the present invention's preparation and high-temperature gas deflation were handled, coating loss was less, even can explain that catalyst coat fastness provided by the invention is good for zero, and coating is not easy to come off more; 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 weight % and 23.5 weight %, and the coating fastness is relatively poor.
Table 2
Visible by table 2, catalyst olefin conversion provided by the invention is higher, and propene yield and propylene selectivity are higher, and amount of coke is lower.
Embodiment 13
According to the method for embodiment 1, the weight ratio of different is silicon oxide substrate and molecular sieve is 1: 99, and the method that provides according to embodiment 1 carries out that loss is 0 after the high temperature deflation.Method according to embodiment 7 is estimated, the result: olefin(e) centent is 13.57% in the product gasoline, and olefin conversion is 63.90; Yield of ethene 1.87 weight %, propene yield 30.19 weight %, ethylene selectivity 2.93%; Propylene selectivity 47.23%, coke are 0.15 gram.
Embodiment 14
Method according to embodiment 2 prepares catalyst; Different is not add dispersant, and its evaluation result is that olefin(e) centent is 21.09 weight % in the product gasoline, and olefin conversion is 43.91 weight %; Yield of ethene 0.75 weight %; Propene yield 18.42 weight %, ethylene selectivity 1.71%, propylene selectivity 41.95%.Coke is 0.26 gram
Claims (11)
1. ordered structure catalyst that is used for steam cracking system propylene hydrocarbon; Said catalyst is made up of the honeycomb substrate of 60～99.9 weight % and the active coating of 0.1～40 weight %; Described active coating comprises molecular sieve and silicon oxide substrate, and said ordered structure catalyst preparation method comprises:
(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, particle diameter mix less than 100nm silica component, add or do not add dispersant, obtain the coating slurries; Wherein said silica component to be particle diameter can form silica less than silica and/or the particle diameter of 100nm less than 100nm presoma material; The content of molecular sieve is 3～60 weight % in the said coating slurries, and the silica component is (with SiO
2Meter) weight ratio with molecular sieve (in butt) 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;
(3) the coating slurries that obtain with step (2) apply honeycomb substrate.
2. according to the described ordered structure catalyst of claim 1, it is characterized in that sieve particle diameter d 90 is 4～8 microns in the molecular sieve pulp that obtains in the step (1).
3. according to the described ordered structure catalyst of claim 1; It is characterized in that; The order that slurries, silica component and the dispersant solution that step (1) is obtained mixes is: in the slurries that step (1) obtains, add the silica component; Stir, add dispersant solution, wherein the weight ratio of dispersant and molecular sieve is 0.01～20: 100.
4. according to the described ordered structure catalyst of claim 3, it is characterized in that the time of said stirring is 15～120 minutes.
5. according to each described ordered structure catalyst of claim 1～4, it is characterized in that the particle diameter of said silica component is 1～60nm, average grain diameter 5～30nm.
6. according to claim 1 or 5 described ordered structure catalysts, it is characterized in that the said presoma material that forms silica is one or more in Ludox, waterglass or the silicon gel.
7. according to each described ordered structure catalyst of claim 1～5, the weight ratio of silica component and molecular sieve is 0.3～25: 100 in the step (2).
8. according to the described ordered structure catalyst of claim 3, 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 0.1～10: 100.
9. according to claim 1,3 or 9 described ordered structure catalysts, it is characterized in that described dispersant is selected from one or more in polyethylene glycol, glycerine, polyvinyl alcohol or the polyacrylic acid.
10. the method for a steam cracking system propylene is included in steam and makes gasoline and each described ordered structure catalyst of claim 1～10 350～900 ℃ of haptoreactions under existing.
11., it is characterized in that the weight ratio of steam and gasoline is 0.01～2: 1 according to the described method of claim 11; The weight (hourly) space velocity (WHSV) of gasoline is 10～350h
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104888843A (en) * | 2015-06-02 | 2015-09-09 | 上海交通大学 | Method for improving efficiency of methanol-to-propylene catalyst |
Citations (3)
| 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 |
| 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 |
| 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 (3)
| 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 |
| 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 |
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888843A (en) * | 2015-06-02 | 2015-09-09 | 上海交通大学 | Method for improving efficiency of methanol-to-propylene catalyst |
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