CN102451739B - Monolithic catalyst for preparing propylene by steam cracking, and application of monolithic catalyst - Google Patents
Monolithic catalyst for preparing propylene by steam cracking, and application of monolithic catalyst Download PDFInfo
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Abstract
The invention relates to a monolithic catalyst for preparing propylene by steam cracking, and application of the monolithic catalyst. The catalyst comprises 60 to 99.9% by weight of cellular carrier and 0.1 to 40% by weight of active coating, wherein the active coating comprises a molecular sieve and an alumina matrix, and the weight ratio of the alumina matrix to the molecular sieve is 0.1 to 30:100. The preparation method of the monolithic catalyst comprises the following steps: (1) preparing a molecular sieve slurry with the particle diameter d90 of 1 to 10 microns; (2) mixing the slurry with an alumina component with the particle diameter of less than 100nm in the presence or absence of a dispersant to obtain a coating slurry; and (3) coating a cellular carrier. The monolithic catalyst containing a molecular sieve composition prepared by the method has the advantages that: the coating is firm and is not easy to fall off, and the service life is long; and the monolithic catalyst is used for preparing propylene by gasoline cracking, and has higher activity, lower coke yield and higher propylene selectivity.
Description
Technical field
The present invention relates to a kind of ordered structure catalyst for steam cracking propylene processed and application thereof.
Background technology
Ordered structure catalyst is a kind of new catalyst, is applied aspect Industrial Catalysis gradually in recent years.For example US Patent No. 4780196 discloses a kind of multi-pore channel honeycomb reactor that utilizes ceramic material to make, and take naphtha as raw material, generates light olefin in 750～850 ℃ of steam heat cracking under the condition that water vapour exists.The method can improve the productive rate of ethene, propylene, reduces the green coke amount.Yet reaction temperature is higher.
In order to introduce catalyst system and catalyzing in the steam cracking reaction process, reduce green coke and reaction temperature, novel ordered structure catalyst generally includes regular carrier and active component coating.US20030070963A1, CN00137253 disclose the method that applies one deck catalyst on tube furnace metal inner pipe wall, and catalyst adopts CaO, Al
2O
3, the oxide such as MgO, have the effect that promotes cracking, reduces green coke.But in the method active component coating easily with the tube wall disengaging, cause catalyst loss.
CN10057772C discloses a kind of regular catalyst for steam cracking, it is characterized in that coating thickness is the composite oxide coating of 1nm～150 μ m on honeycomb support, and described composite oxides are by Al
2O
3And/or SiO
2, and additive form, described additive is selected from one or more the oxide in II A, IIIA, IIIB and IVB family element.The regular catalyst that this invention provides does not contain molecular sieve, and reaction temperature is higher.
CN100448947C discloses a kind of method that reduces olefin(e) centent in gasoline, and olefin containing gasoline is contacted with ordered structure catalyst, in olefin(e) centent, generates propylene, ethene in reducing gasoline.Wherein catalyst used comprises honeycomb support and is distributed in the lip-deep combination of molecular sieve coating of honeycomb support.The preparation method of this catalyst first prepares the combination of molecular sieve particle, then the composition grain ball milling is become slurries and add surfactant-modifiedly, or first uses the surfactant solution modified support, then applies combination of molecular sieve to the honeycomb substrate duct.The introducing of molecular sieve active component has improved the reactivity of catalyst with selective, can reduce the temperature of reaction, but its active component coating fastness is relatively poor, and the use procedure floating coat is easy to come off, and in coating, the content of molecular sieve is difficult to improve.
CN1903808A discloses a kind of method by olefine containing gasoline catalytic cracking propylene processed, comprise with described olefin containing gasoline under water vapour exists with catalyst 450～650 ℃ of haptoreactions, make the olefin cracking in gasoline generate propylene, wherein said catalyst comprises the aluminium oxide of 2～60 % by weight and the modified ZSM-5 zeolite of 40～98 % by weight.Yet the method does not relate to the fastness that improves catalyst coat, and prepared catalyst coat fastness is relatively poor, and the use procedure floating coat is easy to come off, and propene yield is not high.
Summary of the invention
The technical problem to be solved in the present invention is the relatively poor problem of ordered structure catalyst coating fastness that comprises the combination of molecular sieve coating that is used for steam cracking propylene processed for existing, a kind of ordered structure catalyst for steam cracking propylene processed is provided, and the other technical problem that the present invention will solve is to provide the application process of described catalyst.
The invention provides a kind of ordered structure catalyst for steam cracking propylene processed, described catalyst is comprised of the honeycomb substrate of 60～99.9 % by weight and the active coating of 0.1～40 % by weight, described active coating comprises molecular sieve and alumina host, and described ordered structure catalyst preparation method comprises:
(1) molecular sieve is mixed with water, grind, obtain sieve particle diameter d 90 and be the molecular sieve pulp of 1～10 micron;
(2) molecular sieve pulp that step (1) is obtained, particle diameter mix less than the 100nm alumina component, add or do not add dispersant, obtain the coating slurries; To be particle diameter can form the presoma material of aluminium oxide less than aluminium oxide and/or the particle diameter of 100nm less than 100nm to wherein said alumina component; In described coating slurries, the content of molecular sieve is 3～60 % by weight, and alumina component is (with Al
2O
3Meter) weight ratio with molecular sieve (take butt) is 0.1～30: 100, and the weight ratio of dispersant and molecular sieve is 0～20: 100; Described dispersant is selected from one or more in the compound that polyhydroxy, polycarboxylic acids base or polyoxyethylene groups are arranged in molecule;
(3) the coating slurries that obtain with step (2) apply honeycomb substrate.
Wherein the assay method of alumina component particle diameter distribution can adopt light correlation spectroscopy (PCS), referring to ASTM E2490.The measuring method of sieve particle diameter can adopt 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 hydrocarbon ils and ordered structure catalyst provided by the invention 350～900 ℃ of haptoreactions under existing.
Ordered structure catalyst for the steam cracking producing light olefins provided by the invention, comprise honeycomb substrate and combination of molecular sieve coating, coating is firm, is difficult for be full of cracks and comes off, and still has a good fastness in the situation that coating levels is higher, molecular sieve content is higher in coating.Ordered structure catalyst provided by the invention has higher cracking of olefins activity and yield of light olefins, is used for the olefin containing gasoline steam cracking, and olefin conversion is high, and the yield of low-carbon alkene is high, and Propylene Selectivity is high.
The specific embodiment
The ordered structure catalyst of steam cracking producing light olefins provided by the invention is comprised of honeycomb substrate and combination of molecular sieve coating.Described combination of molecular sieve coating is by comprising molecular sieve, alumina component and water, contains or non-dispersant coating slurries apply honeycomb substrate and obtain, and preferred described coating slurries comprise dispersant.Wherein, step is mixed molecular sieve in (1) with water, then grinds and obtains molecular sieve pulp, described grinding can be adopted any existing method, for example can the employing wet ball grinding, it is 1～10 micron that described grinding makes the d90 of sieve particle diameter in slurries, 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 particle size distribution, its implication: in slurries, diameter accounts for 90% of sieve particle cumulative volume in slurries less than the sieve particle volume of this value (d90).
Can molecular sieve pulp, alumina component (aluminium oxide and/or can form the presoma material of aluminium oxide) and dispersant solution be mixed by any existing method in step (2), preferred method is: add aluminium oxide and/or can form the presoma material of aluminium oxide in the molecular sieve pulp that step (1) obtains, stir, preferred mixing time is at least 5 minutes, preferred mixing time is 15～120 minutes, then add dispersant solution to stir, preferably, stirred 10～60 minutes after adding dispersant solution.Described aluminium oxide particles 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 boehmite.
In step (2), the weight that adds of preferred described dispersant solution is 0.01～20 % by weight of molecular sieve butt weight, and preferred addition is 0.05～18 % by weight of molecular sieve butt weight; Wherein in dispersant solution, the content of dispersant is 1～10 % by weight.Described dispersant solution can prepare by the following method:, add 9～99 parts by weight of deionized water and make the dispersant dissolving as 1 weight portion with dispersant, in dispersant solution, the percetage by weight of dispersant is 1～10 % by weight.Described dispersant is selected from all has one or more in the compound of polyhydroxy or polyoxyethylene groups active group in more stable molecule to bronsted lowry acids and bases bronsted lowry, for example for being one or more in polyalcohol type, polyoxyethylene-type or polycarboxylic acids fundamental mode compound, preferably, described dispersant is one or more in polyethylene glycol, glycerine, polyvinyl alcohol or polyacrylic acid.Wherein in dispersant solution, the content of dispersant is 1～10 % by weight, to be particle diameter can form the presoma material of aluminium oxide less than aluminium oxide and/or the particle diameter of 100nm less than 100nm to wherein said alumina component, preferably, the particle diameter of described alumina component is 1～60nm, and average grain diameter (diameter) is preferably 5～45nm; The particle diameter of aluminium oxide and the presoma material that can form aluminium oxide is preferably 1～60nm, more preferably 5～45nm all less than 100nm.
Take the gross weight of coating slurries as benchmark, take the butt molecular sieve content as 3～60 % by weight, be preferably 5～55 % by weight in the coating slurries that step (2) obtains; Alumina component is (with Al
2O
3Meter) be 0.1～30: 100 with the weight ratio of molecular sieve (take butt), be preferably 0.3～25: 100, more preferably 2～25: 100; The weight ratio of dispersant and molecular sieve is 0.01～20: 100, is preferably 0.05～18: 100.The solid content of coating slurries is preferably 3～60 % by weight.
In the honeycomb substrate catalyst that contains the combination of molecular sieve coating provided by the invention, described molecular sieve can be large pore zeolite, one or more in mesopore zeolite and non-zeolite molecular sieve.Described 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 one or more in y-type zeolite, rare earth Y type zeolite (REY), baked rare earth Y type zeolite (CREY), ultrastable (USY), L zeolite, Beta zeolite, modenite and ZSM-18 zeolite, is preferably one or more in y-type zeolite, rare earth Y type zeolite, baked rare earth Y type zeolite, ultrastable and Beta zeolite.Described mesopore zeolite refers to that its cavernous structure opening is at the zeolite of 0.56-0.70 nanometer, it can be selected from one or more in ZSM-5 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, MCM-56 zeolite, preferred ZSM-5 zeolite.described non-zeolite molecular sieve be selected from have the Different Silicon aluminum ratio silicate (as metal silicate metallosilicate, titan silicate titanosilicate), metal aluminate metalloaluminates (as germanium aluminate germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphate metalloaluminophosphates, the silicoaluminophosphate metal integratedsilicoaluminophosphates (MeAPSO and ELAPSO) of metal combination, alumino-silicate silicoaluminophosphates (SAPO), one or more in gallium germanate (gallogermanates), be preferably the SAPO-11 molecular sieve.Described molecular sieve is preferably Y zeolite and/or ZSM-5 zeolite, and described Y zeolite is 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, rare earth modified ZSM-5 zeolite, is for example ZRP zeolite and/or ZSP zeolite.
In the preparation process of the honeycomb substrate catalyst that contains the combination of molecular sieve coating provided by the invention, described coating procedure, can be according to existing method, comprise the coating slurries are contacted with honeycomb substrate, make described coating slurries be full of all ducts of honeycomb substrate, then blow off the carrier outer surface with compressed air, 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, for example the disclosed method of CN1191127C; Described drying can adopt the mode of oven dry, for example dries 2～5 hours preferred 600～700 ℃ of the temperature of described roasting, preferred 1～3 hour of roasting time under 100～120 ℃.Obtain containing the honeycomb substrate catalyst of combination of molecular sieve coating after roasting.Described honeycomb substrate can select commercially available composite oxides honeycomb substrate for example cordierite carrier also can select the honeycomb substrate of other material.
Can also contain clay in coating slurries of the present invention, the weight ratio of described clay and molecular sieve is 0～100: 100; In slurries, the total content of clay and molecular sieve is 3～60 % by weight.Described clay adds in step (2), preferably adds before dispersant, more preferably adds before alumina component.
The ordered structure catalyst of steam cracking provided by the invention propylene processed take the weight of catalyst as benchmark, is comprised of the honeycomb substrate of 60～99.9 % by weight and the active coating of 0.1～40 % by weight; Preferred active coating accounts for 2～35 % by weight, and honeycomb substrate accounts for 65～98 % by weight.In active coating, alumina host is (with Al
2O
3Meter) weight ratio with molecular sieve (take butt) is 0.1～30: 100; Described active coating comprises 70～99.9% molecular sieve, 0.1～30 % by weight alumina hosts, preferred described coating comprises the alumina host of 0.3～25 % by weight and the molecular sieve of 75～99.7 % by weight, more preferably comprises the molecular sieve of 75～99 % by weight and the alumina host of 1～25 % by weight.The coating layer thickness of described catalyst is 1nm～1mm, preferred 1～500 μ m.
The method of steam cracking provided by the invention propylene processed makes hydrocarbon ils and ordered structure catalyst provided by the invention be preferable over 400～650 ℃ of haptoreactions in 350～900 ℃ under steam exists.The weight ratio of steam and gasoline is 0.01～2: 1, preferred 0.1～2: 1; Take coating weight as benchmark, the hydrocarbon ils weight (hourly) space velocity (WHSV) is 10～350h
-1, preferred 10～100h
-1Pressure to reaction does not have specific (special) requirements, and under normal pressure, operation gets final product.Described hydrocarbon ils is boiling point lower than the light hydrocarbons of 350 ℃, for example cracking gasoline, naphtha; Described cracking gasoline is catalytically cracked gasoline or pressure gasoline for example.The method of steam cracking provided by the invention propylene processed is particularly suited for containing the catalytically cracked gasoline propylene processed of alkene, reduces the olefin(e) centent of gasoline product when can produce propylene.
The present invention is further described for the following examples, wherein dispersant used: polyacrylic acid is α reagent company product, and molecular weight 24000 is analyzed pure; Polyethylene glycol: the degree of polymerization 2000, Solution on Chemical Reagents in Shanghai company of traditional Chinese medicines groups, chemical pure; Glycerine, analyze pure, Solution on Chemical Reagents in Shanghai company of traditional Chinese medicines groups.
Embodiment 1
with 108 grams (in butt, lower same) HY type molecular sieve powder (d90=14 micron, technical grade, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product) mix with 120.5 gram deionized waters, wet ball grinding becomes molecular sieve pulp, sieve particle diameter d 90=5 micron, add 128 gram aluminium colloidal sol (salic 21 % by weight in slurries, China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, the pH value is 2.2, particle diameter is 15～45nm, average grain diameter is 30nm), addition in aluminium oxide aluminium colloidal sol is 25 % by weight of molecular sieve weight, stirred 10 minutes, add polyglycol solution 3.24 grams (percetage by weight of polyethylene glycol is 2 % by weight), the addition of this solution is 3 % by weight of molecular sieve weight, stir and obtained catalyst coat in 20 minutes and prepare mix slurry (coating slurries), in slurries, molecular sieve content is 30 % by weight,
Prepare mix slurry with prepared catalyst coat and apply cordierite honeycomb carrier (31 hole/square centimeters, Jiangsu non-metal chemical mechinery works ceramic honey comb subsidiary factory product) all duct inner surfaces, (pressure is 0.4MPa with compressed air, blow off the carrier outer surface down together), under 120 ℃, oven dry is 2 hours, 650 ℃ of lower roastings 1 hour obtain having the honeycomb structured catalyst configurations of molecular sieve catalyst coating.
Be the duct 5 minutes that the honeycomb structured catalyst configurations that obtains is swept in 10 meter per second normal temperature (25 ℃) air wind with flow velocity, weigh, the weight of honeycomb structured catalyst configurations after obtaining normal temperature air and purging; Then be 10 meter per seconds with flow velocity, temperature is to weigh in the duct of the honeycomb structured catalyst configurations that obtains of the warm air blowoff of 400 ℃ in 5 minutes, obtains the weight of honeycomb structured catalyst configurations after warm air blowoff.The weight of honeycomb structured catalyst configurations after the weight of honeycomb structured catalyst configurations and warm air blowoff after after the weight of the honeycomb substrate of uncoated catalyst coat (carrier bare weight), coating supported catalyst, weight, the normal temperature air of honeycomb structured catalyst configurations purge, the results are shown in Table 1.
Embodiment 2
With 120 gram rare earth Y type molecular sieve powder (d90=12 micron, RE
2O
3Content 3 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product) mix with 204 gram deionized waters, wet ball grinding becomes slurries, sieve particle diameter d 90=8 micron in slurries; Add in slurries 144 gram aluminium colloidal sols (salic 10 % by weight, Zhejiang Province Yuda Chemical Co., Ltd's product, particle diameter are 5～15 nanometers, average grain diameter is 10nm, pH value=4), the aluminium oxide addition is 12 % by weight of molecular sieve weight, stirs 15 minutes; Add polyacrylic acid solution 12 grams (polyacrylic acid content is 1 % by weight), the polyacrylic acid solution addition is 10 % by weight of molecular sieve weight, stirs 30 minutes, obtains the catalyst coat slurries, and wherein molecular sieve content is 25 % by weight.Gained catalyst coat slurries are full of all ducts of honeycomb substrate (described honeycomb substrate with embodiment 1, lower with), blow off the carrier outer surface with compressed air, oven dry is 2.5 hours under 120 ℃, 650 ℃ of lower roastings 2.5 hours.
The method purging honeycomb catalyst of describing according to embodiment 1 carries out the deflation experiment, and the results are shown in Table 1.
Embodiment 3
With 180 gram HZSM-5 type molecular sieve powder (silica alumina ratio is 60 for d90=14 micron, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), mix with 122.6 gram distilled water, wet ball grinding becomes slurries, sieve particle diameter d 90=5 micron in slurries; Add 25 gram aluminium colloidal sols (granularity is 35～85 nanometers for salic 36 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, and average grain diameter is 60nm) in slurries, the aluminium oxide addition is 5 % by weight of molecular sieve weight, stirs 60 minutes; (polyethyleneglycol content is 3 % by weight to add polyethylene glycol and polyacrylic acid mixed solution 32.4 grams, polyacrylic acid content is 5 % by weight), the solution addition is 18 % by weight of molecular sieve weight, stir and obtained catalyst coat in 30 minutes and prepare mix slurry, in slurries, molecular sieve content is 50 % by weight.Resulting catalyst coat is prepared all ducts that mix slurry is full of honeycomb substrate, blow off the carrier outer surface with compressed air, oven dry is 1.5 hours under 120 ℃, 650 ℃ of lower roastings 2 hours.
The method purging honeycomb catalyst of describing according to embodiment 1 carries out the deflation experiment, and the results are shown in Table 1.
Embodiment 4
With 100 gram HY molecular sieve powder (d90=14 microns, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product) and 50 gram beta molecular sieve powder (d90=14 microns, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), mix with deionized water 557.5 grams, wet ball grinding becomes slurries, the particle diameter d90=5 micron of molecular sieve in slurries; add 270 gram acidification pseudo-boehmites (salic 10 % by weight in slurries, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, particle diameter is 1～26 nanometer, average grain diameter is 5nm, the pH value is 1.9), the alumina amount that boehmite is introduced accounts for 18 % by weight of molecular sieve weight, stirred 30 minutes, add 22.5 gram glycerine solution (the glycerine weight percentage is 6 % by weight), glycerine solution addition is 15 % by weight of molecular sieve weight, stir and obtained catalyst coat in 10 minutes and prepare mix slurry, wherein molecular sieve content is 15 % by weight.Catalyst coat is prepared all ducts that mix slurry is full of honeycomb substrate (with the described honeycomb substrate of embodiment 1), blow off the carrier outer surface with compressed air, oven dry is 3 hours under 120 ℃, and 650 ℃ of lower 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 table 1.
Embodiment 5
with 160 gram SAPO-11 molecular sieve powder (d90=14 micron, technical grade, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), mix with 142 gram deionized waters, wet ball grinding becomes slurries, particle diameter d90=5 micron, then add wherein 40 gram aluminium colloidal sol (salic 20 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, particle diameter is 15～38nm, average grain diameter is 26nm) and 96 gram acidification pseudo-boehmites (salic 10 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), the aluminium oxide addition is 11 % by weight of molecular sieve weight, stirred 30 minutes, add poly-vinyl alcohol solution 19.2 grams (the polyvinyl alcohol percetage by weight is 1 % by weight), addition is 12 % by weight of molecular sieve weight, stir and obtained catalyst coat in 20 minutes and prepare mix slurry, molecular sieve content is 35 % by weight.Mixed liquor is full of all ducts of honeycomb substrate, blows off the carrier outer surface with compressed air, oven dry is 2 hours under 120 ℃, 650 ℃ of lower roastings 1.5 hours.
The method purging honeycomb catalyst of describing according to embodiment 1 carries out the deflation experiment, and weighing result is listed in table 1.
Embodiment 6
with 180 gram HZSM-5 type molecular sieve powder (silica alumina ratio is 60 for d90=14 micron, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), mix with 122.6 gram distilled water, wet ball grinding becomes slurries, sieve particle diameter d 90=5 micron in slurries, add polyethylene glycol and polyacrylic acid mixed solution 32.4 grams (polyethylene glycol and polyacrylic acid percetage by weight are divided into 3 % by weight and 5 % by weight), addition is 18 % by weight of molecular sieve weight, stirred 30 minutes, then add 25 gram aluminium colloidal sol (salic 36 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, granularity is 35～85 nanometers, average grain diameter is 60nm), the aluminium oxide addition is 5 % by weight of molecular sieve weight, stirred 60 minutes, obtain catalyst coat and prepare mix slurry, in slurries, molecular sieve is 50 % by weight, the d90=5 micron of molecular sieve, the particle diameter of alumina component is 35～85 nanometers, average grain diameter is 60nm.Catalyst coat is prepared all ducts that mix slurry is full of honeycomb substrate, blow off the carrier outer surface with compressed air, oven dry is 1.5 hours under 120 ℃, 650 ℃ of lower roastings 2 hours.
The method purging honeycomb catalyst of describing according to embodiment 1 carries out the deflation experiment, and weighing result is listed in table 1.
Embodiment 7～12
Embodiment 7～12 explanation regular catalysts provided by the invention are used for the effect of steam cracking.
The ordered structure catalyst of embodiment 1～6 method preparation is seated in tubular reactor, then be to contact in reactor with ordered structure catalyst after the olefin containing gasoline of 37.6 % by weight is preheating to 250 ℃ olefin(e) centent, inject simultaneously the water vapour of 250 ℃ of preheatings, the weight (hourly) space velocity (WHSV) that keeps feedstock oil to inject is 20 hours
-1, water/oily charge 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 sees Table 2.
Comparative Examples 1
The ordered structure catalyst that contains molecular sieve coating according to the described method preparation of CN100448947C.
with 100 gram HZSM-5 (with embodiment 3) molecular sieve, boehmite, iron oxide, the active component of lanthana and cerium oxide joins that in deionized water, (wherein molecular sieve content is 75%, matrix content 20%, metal oxide content 5%), regulating pH is 4, make the slurry that solid content is 35 % by weight, then wet ball grinding is to particle diameter d90=5 micron, afterwards 1 gram poly-vinyl alcohol solution (is regulated pH=4 with formic acid in advance, addition is equivalent to molecular sieve butt weight 1.0 % by weight) join in slurry, the method of describing according to embodiment 1 after stirring is prepared into honeycomb structured catalyst configurations, and carry out the deflation experiment according to the method purging honeycomb catalyst that embodiment 1 describes, the results are shown in Table 1.
Comparative Examples 2
With 108 grams (in butt, lower same) HY type molecular sieve powder (d90=14 micron, technical grade, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product) mix with 200 gram deionized waters, add 128 gram aluminium colloidal sol (salic 21 % by weight in slurries, China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, the pH value is 2.2, granularity is 15～45nm, average grain diameter is 30nm), addition in aluminium oxide aluminium colloidal sol is 25 % by weight of molecular sieve weight, and is dry under 120 ℃ after 30 minutes with the homogenizer stirring.
Dried compound particles is levigate with agate mortar, add 200 gram deionized waters, with wet ball grinding to particle diameter d90=5 micron, add afterwards polyglycol solution 3.24 grams (percetage by weight of polyethylene glycol is 2 % by weight), the addition of this solution is 3 % by weight of molecular sieve weight, stir and obtained catalyst coat in 20 minutes and prepare mix slurry (coating slurries), in slurries, molecular sieve content is 30 % by weight.
Prepared catalyst coat is prepared mix slurry be full of honeycomb substrate (cordierite honeycomb carrier, 31 hole/square centimeters, Jiangsu non-metal chemical mechinery works honeycomb pottery subsidiary factory product,) all ducts, blow off the carrier outer surface with compressed air, under 120 ℃, oven dry is 2 hours, and 650 ℃ of lower roastings 1 hour obtain having the honeycomb structured catalyst configurations of molecular sieve catalyst coating.
Be the duct 5 minutes that the honeycomb structured catalyst configurations that obtains is swept in 10 meter per second normal temperature (25 ℃) air wind with flow velocity, weigh, the weight of honeycomb structured catalyst configurations after obtaining normal temperature air and purging; Then be 10 meter per seconds with flow velocity, temperature is to weigh in the duct of the honeycomb structured catalyst configurations that obtains of the warm air blowoff of 400 ℃ in 5 minutes, obtains the weight of honeycomb structured catalyst configurations after warm air blowoff.After after the weight of the honeycomb substrate of uncoated catalyst coat (carrier bare weight), coating supported catalyst, weight, the normal temperature air of honeycomb structured catalyst configurations purge, the weight of honeycomb structured catalyst configurations after the weight of honeycomb structured catalyst configurations and warm air blowoff, list in table 1.
Comparative Examples 3～4
With the ordered structure catalyst that contains molecular sieve coating of Comparative Examples 1～2 method preparation, use the experimental technique identical with embodiment 7～12 to estimate, illustrate that it is used for the effect of steam cracking reaction.Reaction result sees Table 2.
Table 1
By as seen from Table 1, after the catalyst coat of the inventive method preparation is processed through harsh conditions, coating loss is less, even can for zero, illustrate that the coating fastness is good, the coating difficult drop-off, and the catalyst coat loss of existing method preparation is larger, processes through low temperature and high-temperature gas deflation, and loss even can reach 15.9 and 20.8 % by weight, the coating fastness is relatively poor, is easier to come off.
Table 2
By as seen from Table 2, catalyst olefin conversion provided by the invention is higher, and propene yield and Propylene Selectivity are higher.
Embodiment 13
According to the method for embodiment 1, the weight ratio of different is alumina host and molecular sieve is 1: 99, and after high-temperature blowing, loss is 0.Method according to embodiment 7 is estimated, and in the evaluation result product gasoline, olefin(e) centent is 18.54%, and olefin conversion is 50.69, yield of ethene 1.43 % by weight, propene yield 24.35 % by weight, ethylene selectivity 2.85%, Propylene Selectivity 48.54%.
Embodiment 14
Method Kaolinite Preparation of Catalyst according to embodiment 2, different is not add dispersant, method according to embodiment 7 is estimated, its evaluation result is that in product gasoline, olefin(e) centent is 20.15 % by weight, olefin conversion is 46.41 % by weight, yield of ethene 0.88 % by weight, propene yield 19.39 % by weight, ethylene selectivity 1.90%, Propylene Selectivity 41.78%.
Claims (12)
1. ordered structure catalyst that is used for steam cracking propylene hydrocarbon processed, described catalyst is comprised of the honeycomb substrate of 60～99.9 % by weight and the active coating of 0.1～40 % by weight, described active coating comprises molecular sieve and alumina host, and described ordered structure catalyst preparation method comprises:
(1) molecular sieve is mixed with water, grind, obtain sieve particle diameter d 90 and be the molecular sieve pulp of 1～10 micron;
(2) molecular sieve pulp that step (1) is obtained, particle diameter mix less than the 100nm alumina component, add dispersant, obtain the coating slurries; To be particle diameter can form the presoma material of aluminium oxide less than aluminium oxide and/or the particle diameter of 100nm less than 100nm to wherein said alumina component; In described coating slurries, the content of molecular sieve is 3～60 % by weight, with Al
2O
3The alumina component of meter with take the weight ratio of the molecular sieve of butt as 0.1～30: 100, the weight ratio of dispersant and molecular sieve is 0.01～20: 100; Described dispersant is selected from one or more in the compound that polyhydroxy, polycarboxylic acids base or polyoxyethylene groups are arranged in molecule; The order that slurries, alumina component and the dispersant solution that step (1) is obtained mixes is: add alumina component in the slurries that step (1) obtains, stir, add dispersant solution;
(3) the coating slurries that obtain with step (2) apply honeycomb substrate.
2. according to ordered structure catalyst claimed in claim 1, it is characterized in that, in the molecular sieve pulp that step (1) obtains, sieve particle diameter d 90 is 4～8 microns.
3. according to ordered structure catalyst claimed in claim 1, it is characterized in that, wherein the weight ratio of dispersant solution and molecular sieve is 0.1～20: 100.
4. according to ordered structure catalyst claimed in claim 1, it is characterized in that, the time of described stirring is 15～120 minutes.
5. according to ordered structure catalyst claimed in claim 1, it is characterized in that, described alumina component is that particle diameter is less than the presoma material of the formed aluminium oxide of 100nm.
6. according to ordered structure catalyst claimed in claim 5, it is characterized in that, the described presoma material that forms aluminium oxide is aluminium colloidal sol and/or boehmite.
7. according to the described ordered structure catalyst of claim 1～6 any one, it is characterized in that, the particle diameter of described alumina component is 1～60nm, average grain diameter 5～45nm.
8. according to the described ordered structure catalyst of claim 1～5 any one, the weight ratio of alumina component and molecular sieve is 0.3～25: 100.
9. according to ordered structure catalyst claimed in claim 3, it is characterized in that, in described dispersant solution, the concentration of dispersant is 1～10 % by weight; The weight ratio of dispersant solution and molecular sieve is 0.1～10: 100.
10. 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 polyacrylic acid.
11. the method for a steam cracking propylene processed comprises that steam makes hydrocarbon ils and the described ordered structure catalyst of claim 1～10 any one in 350～900 ℃ of haptoreactions under existing.
12. in accordance with the method for claim 11, it is characterized in that, the weight ratio of steam and hydrocarbon ils is 0.01～2: 1; The weight (hourly) space velocity (WHSV) of hydrocarbon ils is 10～350h
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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 |
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