CN103055921A - Catalyst with neat structure for propylene production from steam cracking - Google Patents
Catalyst with neat structure for propylene production from steam cracking Download PDFInfo
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Abstract
A catalyst with neat structure for propylene production from steam cracking is composed of a honeycomb carrier and an active coating. A preparation method of the catalyst comprises steps of: mixing a molecular sieve, a vanadium component, an alkaline earth metal component and water; grinding the mixture to obtain a mixture slurry with particle diameter d90 of 1-10 microns; mixing the mixture slurry with an silicon oxide binder with particle diameter less than 100 nm; adding a dispersant (or not) to obtain a coating slurry; and coating the honeycomb carrier with the obtained coating slurry to obtain the catalyst with neat structure. The catalyst with neat structure can be used for catalytic conversion of oil containing olefin and sulfur hydrocarbon, selectively crack olefin in the raw material to produce propylene, and reduce the sulfur content in gasoline, and has high propylene yield and low coke yield.
Description
Technical field
The present invention relates to a kind of ordered structure catalyst be used to containing alkene and sulphur hydrocarbon ils steam cracking propylene processed and clean gasoline.
Background technology
Ordered structure catalyst (honeycomb substrate catalyst) is applied in the hydrocarbon oil conversion reaction in recent years.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, in the olefin(e) centent, generates propylene, ethene in reducing gasoline.Wherein used regular catalyst comprises honeycomb support and is distributed in the lip-deep combination of molecular sieve coating of honeycomb support, its preparation method is to prepare first the combination of molecular sieve particle, again the composition grain ball milling is become slurries and adds surfactant, or use first the surfactant solution modified support, then apply combination of molecular sieve 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 gasoline conversion, Propylene Selectivity is relatively poor.
CN100404484C discloses a kind of method by olefine containing gasoline catalytic cracking propylene processed, 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 % by weight and the modified ZSM-5 zeolite of 40～98 % by weight.Yet said method does not relate to the problem that reduces content of sulfur in gasoline, and its catalyst is used for sulfur-bearing and olefin gasolines conversion productivity of propylene is not high, and the sulfur content that reduces in the gasoline is limited in one's ability.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of ordered structure catalyst be used to containing alkene and sulphur hydrocarbon ils steam cracking production low-carbon alkene and clean gasoline, and this catalyst can be used for sour gasoline and produces propylene, and can reduce the sulfur content in the gasoline.
The invention provides a kind of ordered structure catalyst be used to containing alkene and hydrocarbon oil containing surphur steam cracking propylene processed and produce simultaneously clean gasoline, described catalyst is comprised of honeycomb substrate and active coating, and described ordered structure catalyst preparation method comprises:
(1) molecular sieve, vanadium component, alkaline earth metal component are mixed with water, grind, obtain particle diameter (d90) and be 1～10 micron mix slurry; With V
2O
5The vanadium component of meter with take the weight ratio of the molecular sieve of butt as 0.1～35: 100, the mol ratio of vanadium and alkaline-earth metal is 10: 1～1: 60;
(2) slurries that step (1) obtained, silica binder component mix, and add or do not add dispersant, obtain the coating slurries; Wherein said silica binder 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 % by weight in the described coating slurries, and the silica binder component is (with SiO
2Meter) weight ratio with molecular sieve (take butt) is 0.1～30: 100, and the weight ratio of dispersant and molecular sieve (take butt) 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 the molecule;
(3) the coating slurries that obtain with step (2) apply honeycomb substrate;
Wherein, in macropore zeolite, mesopore zeolite and non-zeolite molecular sieve one or more of described molecular screening; Described alkaline-earth metal is one or more in beryllium, magnesium, calcium, strontium, barium and the radium.
Ordered structure catalyst provided by the invention, the combination of molecular sieve coating is firm, difficult drop-off in the use procedure, good catalyst activity, alkene in the energy selective cracking raw material is used for containing alkene and the sour gasoline conversion has higher conversion ratio and yield of light olefins, and can reduce sulfur content and olefin(e) centent in the gasoline product, have higher productivity of propylene and Propylene Selectivity, and coke yield is lower.
The specific embodiment
The ordered structure catalyst that contains alkene and sulphur hydrocarbon ils steam cracking propylene processed and clean gasoline provided by the invention, in its preparation process (1) with molecular sieve, the vanadium component, alkaline earth metal component and water mix, then grind and obtain mix slurry, described grinding can be adopted any existing method, for example can adopt wet ball grinding, it is 1～10 micron that described grinding makes the d90 of particle diameter in the slurries, in order to make described ordered structure catalyst have higher reactivity and to have preferably fastness, the d90 of described compound particles diameter is preferably 4～8 microns.The measuring method of described particle diameter can adopt the laser particle analyzer method, referring to ASTM D4464-00 (2005).The D90 value that wherein said particle diameter d90 is 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.Described water is deionized water, decationized Y sieve water or distilled water.
Described molecular sieve, vanadium component, alkaline earth metal component are mixed with water, grind, the material of molecular sieve, the material that contains vanadium, alkaline including earth metal can be added to the water respectively, then grind; Also molecular sieve, the material that contains vanadium and alkaline-earth metal can be added to the water, then grind; Under the preferable case, will contain the compound of vanadium, the compound of alkaline including earth metal, in 600～900 ℃ of roastings, form behind the composite oxides contain vanadium and alkaline-earth metal again and molecular sieve, water mixed grinding.Wherein, the temperature of described roasting is preferably 750～850 ℃; The time of roasting is 0.5～100 hour, preferred 1～10 hour.
The described material that contains vanadium is inorganic compound or in the organic compound one or more of vanadium for example, for example for vanadic anhydride, ammonium metavanadate, contain in the composite oxides of vanadium and alkaline-earth metal one or more.Take the butt weight of active coating slurries as benchmark, the consumption of vanadium component makes in the resulting active coating and contains with V
2O
5The content of the vanadium component of meter is 0.1～25 % by weight, is preferably 0.2～10 % by weight.
Described alkaline-earth metal is selected from one or more in beryllium, magnesium, calcium, strontium, the barium, is preferably magnesium and/or calcium.The mol ratio of vanadium and alkaline-earth metal is 10: 1～1: 60, is preferably 4: 1～1: 40.The material of described alkaline including earth metal is one or more in the chloride, nitrate, sulfate, acylate of alkaline-earth metal for example, wherein are preferably nitrate or chloride.
Molecular sieve of the present invention can be large pore zeolite, one or more in mesopore zeolite and the 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 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, be preferably in y-type zeolite and the Beta zeolite one or more, described y-type zeolite is one or more in HY type zeolite, rare earth Y type zeolite, baked rare earth Y type zeolite, the ultrastable for example.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 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.Described non-zeolite molecular sieve be selected from have the Different Silicon aluminum ratio silicate (such as metal silicate metallosilicate, titan silicate titanosilicate), metal aluminate metalloaluminates (such as germanium aluminate germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphate metalloaluminophosphates, the silicoaluminophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO) of metal combination, alumino-silicate silicoaluminophosphates (SAPO), in the gallium germanate (gallogermanates) one or more are preferably the SAPO-11 molecular sieve.Described molecular sieve is preferably one or more in β zeolite, Y zeolite and the ZSM-5 zeolite; 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, the rare earth modified ZSM-5 zeolite, for example is ZRP zeolite and/or ZSP zeolite.
The preferred dispersant that adds in the step (2), the weight ratio of dispersant and molecular sieve is 0.01～20: 100.Can be by any existing method with mix slurry, silica binder component (silica and/or can form the presoma material of silica) and dispersant solution mix, preferred method is: add silica and/or can form the presoma material of silica in the mix slurry that step (1) obtains, stir, preferred mixing time is at least 5 minutes, preferred mixing time is 15～120 minutes, then adding dispersant solution stirs, stirred 10～60 minutes behind the preferred adding dispersant solution, the presoma material that can form silica can be selected from Ludox, one or more in the waterglass.Wherein the content of dispersant is 1～10 % by weight in the dispersant solution.Described silica binder component is particle diameter less than the silica of 100nm and/or can forms the presoma material of silica, and preferred, the particle diameter of described silica binder component is 1～60nm, and average grain diameter (diameter) is preferably 5～30nm; Described particle diameter all less than 100nm, is preferably 1～60nm, more preferably 5～30nm less than the silica of 100nm and the particle diameter of presoma material that can form silica.The described presoma material that forms silica is one or more in Ludox, waterglass or the silicon gel.The assay method that silica binder component particle diameter of the present invention distributes can adopt ASTM E2490, i.e. light correlation spectroscopy (PCS).
In the step (2), preferably add aqueous dispersant, the adding weight of described dispersant solution is 0.01～20 % by weight of molecular sieve butt weight, and more preferably addition is 0.05～18 % by weight of molecular sieve butt weight; Wherein the percetage by weight of dispersant is 1～10 % by weight in the dispersant solution.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, the percetage by weight that obtains dispersant is the dispersant solution of 1～10 % by weight.Described dispersant is selected from all has in the compound of polyhydroxy or polyoxyethylene groups active group one or more in the more stable molecule to bronsted lowry acids and bases bronsted lowry, for example be in polyalcohol type, polyoxyethylene-type or the polycarboxylic acids fundamental mode compound one or more, preferably, described 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, vanadium component, alkaline earth metal component silica binder component, dispersant solution and water, the consumption of each component makes in the slurries that obtain, take the gross weight of coating slurries as benchmark, molecular sieve content (take butt) is 3～60 % by weight, be preferably 5～55 % by weight, the silica binder component is (with SiO
2Meter) is 0.1～30: 100 with the weight ratio of molecular sieve (take 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.With V
2O
5The weight ratio of meter vanadium component and molecular sieve is 0.1～35: 100, is preferably 1～15: 100, more preferably 3～10: 100; The mol ratio of described vanadium and alkaline-earth metal is 4: 1～1: 40.The solid content of described coating slurries preferably is no more than 61 % by weight, more preferably 4～60 % by weight.
In the ordered structure catalyst preparation process provided by the invention, the described coating honeycomb substrate of step (3), can carry out according to existing method, generally include 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.Described honeycomb substrate can select commercially available composite oxides honeycomb substrate for example cordierite carrier also can select the honeycomb substrate of other material.Describedly blow off the method for carrier outer surface with compressed air, can be according to existing method, the disclosed method of CN1191127C for example.Described drying can adopt the mode of oven dry, for example in 100～120 ℃ of lower oven dry 2～5 hours, preferred 600～700 ℃ of the temperature of described roasting, preferred 1～3 hour of roasting time.Obtain containing the ordered structure catalyst of combination of molecular sieve active coating and honeycomb substrate after the roasting, wherein said active coating comprises molecular sieve, be derived from the vanadium matrix of described vanadium component, be derived from the alkaline-earth metal matrix of described alkaline earth metal component and be derived from the silica binder of described silica binder component.
The ordered structure catalyst of steam cracking provided by the invention propylene processed take the weight of catalyst as benchmark, preferably is comprised of the honeycomb substrate of 60～99.9 % by weight and the active coating of 0.1～40 % by weight; More preferably active coating accounts for 2～35 % by weight, and honeycomb substrate accounts for 65～98 % by weight.Described active coating preferably includes 65～99% molecular sieve, with V
2O
5The meter 0.1～25 % by weight vanadium matrix, in the alkaline-earth metal matrix of oxide 0.1～25 % by weight with SiO
2Meter 0.1～30 % by weight silica binder; Preferred described coating comprises the silica binder of 0.3～20 % by weight, the molecular sieve of 70～95 % by weight, the vanadium matrix of 0.2～10 % by weight and the alkaline-earth metal matrix of 0.1～20 % by weight; More preferably comprise the molecular sieve of 75～90 % by weight and the silica binder of 1～15 % by weight, the V of 2～10 % by weight
2O
5, 0.5～10 % by weight alkaline-earth metal.The coating layer thickness of described catalyst can be selected as required, and for example its thickness can be 1nm～1mm, usually is no more than 500 μ m, is preferably 1～500 μ m.
Preferably also introduce other metal component in the active coating slurries of ordered structure catalyst provided by the invention, this other metal component is one or more in IIIA family metal, IVA family metal, IIB family metal, IVB family metal, VB family metal, group vib metal, VIII family metal and the rare earth compound except vanadium.Described other metal is preferably one or more in gallium, indium, thallium, germanium, tin, zinc, cadmium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, iron, cobalt, nickel, the lanthanide rare metal, described lanthanide rare metal finger lanthanum, cerium, lanthanum rich norium or cerium-rich mischmetal metal.Described other inorganic oxide matrix was introduced before described silica binder component, under the preferable case, described other metal component mixes with vanadium and alkaline-earth metal and is incorporated in the described coating slurries after forming the composite oxides contain vanadium and alkaline-earth metal.Take the butt weight of catalyst activity coating as benchmark, in oxide, it is 0～20 % by weight that the introducing amount of described other metal component makes the content of the metal matrix that is derived from described other metal component in the active coating that obtains, and the content of described other metal matrix is preferably 0.5～10 % by weight.
Also can contain other inorganic oxide matrix in the active coating of ordered structure catalyst provided by the invention, take the butt weight of active coating as benchmark, take the content of described other inorganic oxide matrix of oxide as 0～30 % by weight, preferably be no more than 25 % by weight, more preferably no more than 10 % by weight.Described other inorganic oxide matrix is selected from one or more in aluminium oxide, silica, amorphous aluminum silicide and the clay.The d90 of described inorganic oxide matrix is 1～10 micron, is preferably 4～8 microns.The weight ratio of described inorganic oxide matrix and molecular sieve is 0～60: 100, is preferably 0～40: 100.Described clay can be selected from kaolin, halloysite, imvite, diatomite, tired in the soil one or more, the preferred kaolin of taking off.Described alumina host is one or more in gama-alumina, η-aluminium oxide, the κ aluminium oxide for example, and described silica binder is silochrom for example.When preparing in such cases the coating slurries, described electrodeless matrix of oxide is introduced in step (1) or (2), preferably before dispersant, introduce, more preferably before the silica binder component, add, more described inorganic oxide is mixed being incorporated in the described coating slurries after forming the composite oxides contain vanadium and alkaline-earth metal with vanadium and alkaline-earth metal.
The invention provides the hydrocarbon ils cracking catalyst propylene processed that ordered structure catalyst is applicable to sulfur-bearing and alkene, described hydrocarbon ils is catalytically cracked gasoline for example.
Embodiment 1
(1) with 108 gram HY type molecular sieve (in butt) powder (d90=14 micron, technical grade, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product) and 3.86 gram ammonium metavanadate (NH
4VO
3, chemical pure, the Beijing Chemical Plant produces), 55.5 gram anhydrous nitric acid magnesium (Mg (NO
3)
2, chemical pure, the Beijing Chemical Plant produces) and 834.2 restrain deionized waters and mix, wet ball grinding becomes slurries, compound particles diameter d 90=5 micron;
(2) in the slurries that step (1) obtains, add 180 gram waterglass (silicon oxide-containing 15 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, modulus is 3.2, particle diameter is 1～5nm, average grain diameter is 3nm), addition in silica waterglass is 25 % by weight of HY molecular sieve weight, stirred 10 minutes, add polyglycol solution 3.24 grams (percetage by weight of polyethylene glycol is 2 % by weight in the solution), the addition of this solution is 3 % by weight of molecular sieve weight, stirs to obtain catalyst coat in 20 minutes and prepare mix slurry (coating slurries).
Prepare mix slurry with prepared catalyst coat and apply honeycomb substrate (cordierite honeycomb carrier, 31 hole/square centimeters, Jiangsu non-metal chemical mechinery works honeycomb pottery subsidiary factory product) all duct inner surfaces, (pressure is 0.4MPa with compressed air, lower with) blow off the honeycomb substrate outer surface, 120 ℃ of lower oven dry 2 hours, 650 ℃ of lower roastings 1 hour, obtain having the ordered structure catalyst C1 of molecular sieve catalyst coating, its coating levels is 5.5%.See Table 1-1.
Embodiment 2
(1) 11 gram ammonium metavanadates (specification is with embodiment 1), 13.9 gram anhydrous nitric acid magnesium (specification is with embodiment 1) are mixed, the solid mixture that obtains 800 ℃ of roastings 2 hours, is obtained containing the composite oxides VA1 of vanadium and alkaline-earth metal.The composition of VA1 is listed among the table 1-1;
(2) the composite oxides VA1 that (1) is obtained and 120 gram rare earth Y type molecular sieves (in butt, lower same) powder (d90=12 micron, RE
2O
3Content 3 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product) and 252 gram deionized waters mixing, wet ball grinding becomes slurries, the particle diameter d90=8 micron of slurries;
(3) in the slurries that (2) obtain, add 30 gram Ludox (silicon oxide-containing 20 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, the particle diameter of Ludox is 12～35nm, average grain diameter is 20nm), the silica amount of being introduced by Ludox is 5 % by weight of molecular sieve weight, stirs 60 minutes; Add polyethylene glycol and polyacrylic acid mixed solution 21.6 grams (polyethyleneglycol content is 3 % by weight, and polyacrylic acid content is 5 % by weight), the solution addition is 18 % by weight of molecular sieve weight, stirs to obtain the catalyst coat slurries in 30 minutes.
Gained catalyst coat slurries are full of all ducts of honeycomb substrate (described honeycomb substrate is with embodiment 1), blow off the carrier outer surface with compressed air, 120 ℃ of lower oven dry 2.5 hours, 650 ℃ of lower roastings 2.5 hours, the ordered structure catalyst C2 that obtains having the molecular sieve catalyst coating.Coating levels is 7.6%, and thickness is 89 microns.
Embodiment 3～4
(1) method by (1) among the embodiment 2 prepares the composite oxides that contain vanadium component and alkaline earth metal component, different is to replace anhydrous nitric acid magnesium with 23.2 gram anhydrous nitric acid calcium or with 23.9 mixtures that restrain anhydrous nitric acid magnesium and 7.8 gram anhydrous nitric acid calcium respectively, must contain composite oxides VA2 and the VA3 of vanadium component and alkaline earth metal component.The composition of VA2～VA3 is listed among the table 1-1.
(2) press the method prepared slarry of (2) among the embodiment 2, different is to replace VA1 with VA2 and VA3 respectively, (lattice constant is 24.35 dusts to use respectively overstable gamma zeolite, sodium oxide molybdena is 0.5 % by weight, the Zhou village catalyst plant is produced) or the mixture of above-mentioned overstable gamma zeolite and ZSM-5 zeolite (weight ratio of overstable gamma zeolite and ZSM-5 zeolite is 8: 1, the sodium oxide content of ZSM-5 zeolite is weight 0.1 % by weight, and silica alumina ratio is 30, and the Zhou village catalyst plant is produced) the replacement rare earth exchanged Y zeolite.
(3) press the method Kaolinite Preparation of Catalyst of (3) among the embodiment 2, different is to add polyacrylic acid solution 12 grams (polyacrylic acid content is 1 % by weight) in slurries, the polyacrylic acid solution addition is 10 % by weight of molecular sieve weight, stirs 30 minutes, obtains the catalyst coat slurries.Gained catalyst coat slurries are full of all ducts of honeycomb substrate (described honeycomb substrate is with embodiment 1), blow off the carrier outer surface with compressed air, 120 ℃ of lower oven dry 2.5 hours, 650 ℃ of lower roastings 2.5 hours, the ordered structure catalyst C3～C4 that obtains having the molecular sieve catalyst coating.
Embodiment 5～10
The following examples illustrate Catalysts and its preparation method provided by the invention.
(1) method by (1) among the embodiment 2 prepares the composite oxides that contain vanadium and alkaline-earth metal, and difference is respectively:
1), in the mixture of ammonium metavanadate, anhydrous nitric acid magnesium, also added the anhydrous nitric acid zinc (chemical pure, the Beijing Chemical Plant produces) of 5.9 grams.
2), in the mixture of ammonium metavanadate, anhydrous nitric acid magnesium, suspension 62.7 grams that also added rare-earth hydroxide, contain rare earth oxide 25 % by weight in this suspension, wherein lanthana accounts for 23 % by weight of rare earth oxide, cerium oxide accounts for 67 % by weight of rare earth oxide, and other rare earth oxides account for 10 % by weight of rare earth oxide.This suspension is (RE in 42.6 gram rare earth-iron-boron (Gansu Rare Earth Co.'s product) aqueous solution
2O
3Concentration 36.73 % by weight) add 2.1 kilograms of concentrated ammonia liquors (concentration 17 % by weight), the suspension that the rare earth ion precipitation is formed; Ammonium metavanadate (specification is with embodiment 1) consumption is 15.3 grams, and anhydrous nitric acid magnesium (specification is with embodiment 1) consumption is 4.8 grams.
3), in the mixture of ammonium metavanadate, anhydrous nitric acid magnesium, 28.2 milliliters of zirconium oxychloride (brilliant Anhua, the Jiangxi worker Co., Ltd produces) aqueous solution and 3.14 that also added concentration and be 2.0 mol/L restrain anhydrous calcium chlorides.
4) in the mixture of ammonium metavanadate, anhydrous nitric acid magnesium, also added concentration and be 34.4 milliliters of iron chloride (chemical pure, the Beijing Chemical Plant produces) aqueous solution of 2.0 mol/L; Ammonium metavanadate (specification is with embodiment 1) consumption is 14.6 grams, and anhydrous nitric acid magnesium (specification is with embodiment 1) consumption is 27.8 grams.
5), in the mixture of ammonium metavanadate, anhydrous nitric acid magnesium, also added concentration and be 31.3 milliliters of gallium chloride (chemical pure is produced) aqueous solution of 2 mol/L.
6), in the mixture of ammonium metavanadate, anhydrous nitric acid magnesium, also added kaolin (butt) 4.8 gram.
Obtain containing the composite oxides VA4 of vanadium and alkaline-earth metal, VA5, VA6, VA7, VA8, VA9.The composition of VA4～VA9 is listed among the table 1-2.
(2) press the method Kaolinite Preparation of Catalyst of embodiment 2, different is to use respectively VA4, VA5, and VA6, VA7, VA8, VA9 replaces VA1, obtains catalyst provided by the invention, obtains ordered structure catalyst C5～C10.
Embodiment 11
Press the method Kaolinite Preparation of Catalyst of embodiment 2, be not both with 180 gram HZSM-5 type molecular sieve powder (d90=14 micron, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, silica alumina ratio (Si
2O
3/ Al
2O
3Mol ratio) be 60) replace rare earth Y type molecular sieve, wet ball grinding becomes slurries, particle diameter d90=5 micron in the slurries; In slurries, add 45 gram Ludox (silicon oxide-containing 20 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, the particle diameter of Ludox is 12～35nm, average grain diameter is 20nm), the silica amount of being introduced by Ludox is 5 % by weight of molecular sieve weight, stirs 60 minutes; Add polyethylene glycol and polyacrylic acid mixed solution 32.4 grams (polyethyleneglycol content is 3 heavy %, and polyacrylic acid content is 5 % by weight), the solution addition is 18 % by weight of molecular sieve weight, stirs to obtain catalyst coat in 30 minutes and prepare mix slurry.Preparing mix slurry with resulting catalyst coat applies honeycomb substrate and obtains (120 ℃ of lower oven dry 1.5 hours, 650 ℃ lower roasting 2 hours) and obtain ordered structure catalyst C11.Coating levels 40.02%.
Embodiment 12
Press the method Kaolinite Preparation of Catalyst of embodiment 2, different is with 100 gram DASY0.0 type 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) replaces rare earth Y type molecular sieve, wet ball grinding becomes slurries, the particle diameter d90=5 micron in the slurries; Then add 80 gram silicon gel (silicon oxide-containing 15 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, the viscosity of silicon gel is 600cst (25 ℃), granularity is 5～15 nanometers, average grain diameter is 12nm), the silica addition is 12 % 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, stirs to obtain the catalyst coat slurries in 10 minutes.The catalyst coat slurries are full of all ducts of honeycomb substrate, blow off the carrier outer surface with compressed air, 120 ℃ of lower oven dry 3 hours, 650 ℃ of lower roastings 1 hour obtain ordered structure catalyst C12.Coating levels 3.6%.
Embodiment 13
Press the method Kaolinite Preparation of Catalyst of embodiment 2, different is that 160 gram SAPO-11 molecular sieve powder (d90=14 micron, technical grade, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product) are replaced rare earth Y type molecular sieve, wet ball grinding becomes slurries, particle diameter d90=5 micron; Then to wherein adding 50 gram Ludox (silicon oxide-containing 22 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, the silica sol particle diameter is 5～15nm, average grain diameter is 10nm) and 44 gram silicon gel (silicon oxide-containing 15 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, the viscosity of silicon gel is 600cst (25 ℃), the particle diameter scope is 5～15 nanometers, average grain diameter is 12nm), the silica 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, stirs to obtain the catalyst coat slurries in 20 minutes.Resulting coating solution is full of all ducts of honeycomb substrate, blows off the carrier outer surface with compressed air, 120 ℃ of lower oven dry 2 hours, 650 ℃ of lower roastings 1.5 hours obtain ordered structure catalyst C13.Coating levels 17.9%.
Embodiment 14
Press the method Kaolinite Preparation of Catalyst of embodiment 2, different is with 180 gram HZSM-5 type molecular sieve powder (d90=14 microns, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, silica alumina ratio is 60) replace the rare earth Y type molecular sieve wet ball grinding to become slurries, particle diameter d90=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 % by weight and 5 % by weight), addition is 18 % by weight of molecular sieve weight, stirred 30 minutes, then add 45 gram Ludox (silicon oxide-containing 20 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, the silica sol particle diameter is 12～35nm, average grain diameter is 20nm), the silica addition is 5 % by weight of molecular sieve weight, stirred 60 minutes, and obtained the catalyst coat slurries.The catalyst coat slurries are full of all ducts of honeycomb substrate, blow off the carrier outer surface with compressed air, 120 ℃ of lower oven dry 1.5 hours, 650 ℃ of lower roastings 2 hours.Obtain ordered structure catalyst C14.Coating levels 8.3%.
Embodiment 15～28
Embodiment 15～28 explanations regular catalyst provided by the invention is used for the effect of steam cracking.
The ordered structure catalyst that provides among the embodiment 1～14 is seated in the tubular reactor, then be 37.6 % by weight with olefin(e) centent, sulfur content is to contact in reactor with ordered structure catalyst after the olefin containing gasoline of 628 μ g/g is preheating to 250 ℃, 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 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 sees Table 2.
Table 1-1
| The embodiment numbering | 1 | 2 | 3 | 4 |
| The composite oxides numbering that contains vanadium and alkaline-earth metal | VA1 | VA2 | VA3 | |
| The composite oxides that contain vanadium and alkaline-earth metal form | ||||
| The vanadium constituent content, % by weight is (with V 2O 5) meter | 69.4％ | 51.9％ | 57.1％ | |
| The magnesium constituent content, % by weight (in MgO) | 30.6％ | 48.1％ | 25.1％ | |
| The calcium constituent content, % by weight (in CaO) | 17.7％ | |||
| The mol ratio of vanadium and alkaline-earth metal | 1∶1 | 2∶3 | 2∶3 | |
| The catalyst numbering | C1 | C2 | C3 | C4 |
| The catalyst activity coating levels, % by weight | 5.5 | 7.6 | 7.4 | 7.7 |
| The deflation loss amount, % by weight | 0 | 0 | 0 | 0 |
Table 1-2
Wherein said deflation, be the duct 5 minutes that the ordered structure catalyst that obtains is swept in 10 meter per second normal temperature (25 ℃) air wind with flow velocity, then be 10 meter per seconds with flow velocity, temperature is to weigh in the duct of the ordered structure catalyst that obtains of 400 ℃ warm air blowoff in 5 minutes, obtains the weight of ordered structure catalyst after the warm air blowoff.(catalyst weight before the catalyst weight/deflation after the 1-deflation) * 100% is designated as the deflation loss amount.
Comparative Examples 1
(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) and 3.86 gram ammonium metavanadate (NH
4VO
3, chemical pure, the Beijing Chemical Plant produces), 55.5 gram anhydrous nitric acid magnesium (Mg (NO
3)
2, chemical pure, the Beijing Chemical Plant produces) and 834.2 restrain deionized waters and mix;
(2) in the slurries that step (1) obtains, add 180 gram waterglass (silicon oxide-containing 15 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, modulus is 3.2, particle diameter is 1～5nm, average grain diameter is 3nm), addition in silica waterglass is 25 % by weight of molecular sieve weight, stirs to obtain mix slurry in 30 minutes; This mix slurry spray-drying is obtained microballoon, thus obtained microsphere was in 600 ℃ of roastings 2 hours, then mix making beating with 950 gram water, wet ball grinding, obtain particle diameter d90 and be 5 microns slurries, add therein polyglycol solution 3.24 grams (percetage by weight of polyethylene glycol is 2 % by weight in the solution), then the method coating honeycomb substrate according to embodiment 1 obtains contrast medium D1.Its deflation loss amount is 21.5%.
Table 2
Comparative Examples 2
Method according to embodiment 15 is estimated the D1 catalyst, the results are shown in Table 2.
Comparative Examples 3
Method Kaolinite Preparation of Catalyst D2 according to Comparative Examples 1, different is not contain vanadium and alkaline-earth metal in the catalyst, and then according to the method evaluation of embodiment 15, its reaction result: sulfur content is 552 μ g/g in the product gasoline, coke is 0.21 gram, and propene yield is 20.13%.
Table 2 (continuing)
By as seen from Table 2, ordered structure catalyst provided by the invention has higher Propylene Selectivity and productivity of propylene, has higher sulphur conversion capability and alkene conversion capability, be used for containing the gasoline vapor cracking reaction of alkene and sulfide, can reduce sulfur content and olefin(e) centent in the gasoline.
Claims (14)
1. ordered structure catalyst that is used for containing alkene and sulphur hydrocarbon ils steam cracking propylene processed and clean gasoline, described ordered structure catalyst is comprised of honeycomb substrate and active coating, and described ordered structure catalyst preparation method comprises:
(1) molecular sieve, vanadium component, alkaline earth metal component are mixed with water, grind, obtain particle diameter d90 and be 1～10 micron mix slurry, the mol ratio of vanadium and alkaline-earth metal is 10: 1～1: 60, with V
2O
5The vanadium component of meter with take the weight ratio of the molecular sieve of butt as 0.1～35: 100;
(2) slurries that step (1) obtained, silica binder component mix, and add or do not add dispersant, obtain the coating slurries; Wherein said silica binder 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 % by weight in the described coating slurries, with SiO
2The silica binder 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 0～20: 100; Described 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;
Wherein, in macropore zeolite, mesopore zeolite and non-zeolite molecular sieve one or more of described molecular screening; Described alkaline-earth metal is one or more in beryllium, magnesium, calcium, strontium, barium and the radium.
2. according to ordered structure catalyst claimed in claim 1, it is characterized in that the weight ratio of described vanadium component and molecular sieve is 0.2～15: 100; The weight ratio of described silica binder component and molecular sieve is 0.3～25: 100.
3. according to ordered structure catalyst claimed in claim 1, it is characterized in that the mol ratio of described vanadium and alkaline-earth metal is 4: 1～1: 40.
4. according to each described ordered structure catalyst of claim 1～3, it is characterized in that, take the weight of active coating as benchmark, comprise the molecular sieve of 65～99 % by weight in the described active coating.
5. according to ordered structure catalyst claimed in claim 4, it is characterized in that, comprise the molecular sieve of 70～95 % by weight in the described active coating.
6. according to ordered structure catalyst claimed in claim 1, it is characterized in that in y-type zeolite, Beta zeolite and ZSM-5 zeolite one or more of described molecular screening.
7. according to ordered structure catalyst claimed in claim 1, it is characterized in that described silica binder component is one or more in Ludox, waterglass or the silicon gel.
8. according to claim 1 or 7 described ordered structure catalysts, it is characterized in that the particle diameter of described silica binder component is 1～60nm, average grain diameter 5～30nm.
9. according to ordered structure catalyst claimed in claim 1, it is characterized in that, in the slurries that step (1) obtains, add silica in the step (2) and/or can form the presoma material of silica, stir, then add dispersant solution, stir.
10. according to claim 1 or 9 described ordered structure catalysts, it is characterized in that add dispersant solution in the step (2), the concentration of dispersant is 0.1～10 % by weight in the dispersant solution; The weight ratio of dispersant solution and molecular sieve is 0.1～20: 100.
11. according to claim 1 or 9 or 10 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.
12. according to ordered structure catalyst claimed in claim 1, it is characterized in that, described vanadium component be vanadic anhydride, ammonium vanadate or contain vanadium and the composite oxides of alkaline-earth metal in one or more; Described alkaline earth metal component be chloride, nitrate, sulfate, the acylate of alkaline-earth metal and contain vanadium and the composite oxides of alkaline-earth metal in one or more.
13., it is characterized in that the active coating of this catalyst contains inorganic oxide matrix and/or other metal matrix according to claim 1,4 or 5 described ordered structure catalysts; Described other metal is one or more in IIIA family metal, IVA family metal, IIB family metal, IVB family metal, VB family metal, group vib metal, VIII family metal and the rare earth metal except vanadium, take the weight of catalyst activity coating as benchmark, in oxide, the content of other metal matrix is 0～20 % by weight in the described active coating, in oxide, the content of described inorganic oxide matrix is 0～30 % by weight.
14., it is characterized in that described other metal is one or more in gallium, indium, thallium, germanium, tin, zinc, cadmium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, iron, cobalt, nickel, the lanthanide rare metal according to the described ordered structure catalyst of claim 13.
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