CN103059907B - Method for reducing alkene and sulfur content in gasoline and method for producing propylene - Google Patents
Method for reducing alkene and sulfur content in gasoline and method for producing propylene Download PDFInfo
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- CN103059907B CN103059907B CN201110318696.9A CN201110318696A CN103059907B CN 103059907 B CN103059907 B CN 103059907B CN 201110318696 A CN201110318696 A CN 201110318696A CN 103059907 B CN103059907 B CN 103059907B
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Abstract
The invention relates to a method for reducing alkene and sulfur content in gasoline and a method for producing propylene, which comprises a step that the gasoline containing alkene and sulfur enables a contact reaction with a structured catalyst composed of a cellular carrier and an active coating, the active coating comprises a molecular sieve, a vanadium matrix, an alkaline earth metal matrix and a silicon oxide binder; wherein the mol ratio of vanadium and alkaline earth metal is 10:1-1:60. The molecular sieve is one or more selected from macroporous zeolite, mesoporous zeolite and nonzeolite molecular sieve; and the alkaline earth metal is one or more selected from beryllium, magnesium, calcium, strontium, barium and radium. The method can selectively crack the alkene in a raw material for producing propylene, the sulfur content in the gasoline is reduced, and the method has high propylene yield.
Description
Technical field
The present invention relates to a kind of method containing alkene and sulfur oil steam cracking propylene and clean gasoline.
Background technology
Require more and more stricter to the sulphur content of vehicle fuel and olefin(e) centent in world wide.The gasoline of China 85% comes from catalytic cracking, and catalytically cracked gasoline contains a large amount of alkene and sulphur, is difficult to the requirement meeting gasoline standard, usually needs to be used as vehicle fuel after treatment.At present, the method removing sulphur in sour gasoline normally carries out weighted BMO spaces to stock oil, or refines the object reaching and reduce sulfur in gasoline after carrying out hydrogenation to gasoline.But these two kinds of method investments are large, and under high pressure operate, process cost is high, and is not suitable for reduction content of olefin in gasoline, cannot for the production of propylene.
CN100404484C discloses a kind of method by olefine containing gasoline catalytic cracking propylene, to comprise described olefine contained gasoline in the presence of water vapor with catalyzer 450 ~ 650 DEG C of contact reactss, make the olefin cracking in gasoline generate propylene, wherein said catalyzer comprises the aluminum oxide of 2-60 % by weight and the modified ZSM-5 zeolite of 40-98 % by weight.But aforesaid method does not relate to and reduces the problem of content of sulfur in gasoline, its for sulfur-bearing and olefin gasolines converting propylene productive rate not high, sulphur weak effect falls.
It is little that ordered structure catalyst has pressure drop, the feature that air speed is high, is applied gradually in recent years in hydrocarbon oil conversion reaction.Such as CN100448947C discloses a kind of method reducing olefin(e) centent in gasoline, is contacted by olefine contained gasoline with ordered structure catalyst, in reduction gasoline while olefin(e) centent, generates propylene, ethene.Regular catalyst wherein used comprises honeycomb support and is distributed in the combination of molecular sieve coating on honeycomb support surface, its preparation method first prepares molecular sieve combination composition granule, again composition grain ball milling become slurries and add tensio-active agent, or first use surfactant soln modified support, then apply combination of molecular sieve on honeycomb substrate duct.But the method does not relate to sulfur-bearing and olefin gasolines transforms, reduce content of sulfur in gasoline weak effect, and the selectivity of its propylene is poor.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of for transforming the method for producing propylene and clean gasoline containing alkene and sulfur oil, and the method uses ordered structure catalyst, can reduce the olefin(e) centent in gasoline and sulphur content, and produce propylene.
The invention provides a kind of reduce sulfur in gasoline and olefin(e) centent and prepare propylene containing alkene and sulfur oil method for transformation, comprising in the presence of water vapor will containing alkene and sulfur oil and ordered structure catalyst contact reacts, wherein said ordered structure catalyst is made up of honeycomb substrate and activated coating, and wherein said activated coating comprises molecular sieve, vanadium matrix, alkaline-earth metal matrix and silica binder.
Preferably, described ordered structure catalyst contains molecular sieve, 0.1-25 % by weight V of 65-99 % by weight
2o
5, 0.1-20 % by weight alkaline earth metal oxide and 0.1-30 % by weight silica binder.
Method provided by the invention, in the presence of water vapor will containing alkene and sulfur oil and ordered structure catalyst contact reacts, and the temperature of reaction is 400-650 DEG C, preferred 450-650 DEG C, and weight hourly space velocity is 1-1000h
-1, preferred 3-500h
-1, steam and the described weight ratio containing alkene and sulfur oil are 0.02-3: 1.Method for transformation provided by the invention, use ordered structure catalyst, can operate at lower pressures, the present invention does not have particular requirement to pressure, and its pressure can be normal pressure-1Mpa usually, generally operates under 0.01-0.7MPa.
Provided by the invention containing alkene and sulfur oil method for transformation, use the ordered structure catalyst containing activated coating, there is higher olefin conversion and yield of light olefins, the sulphur content in gasoline product and olefin(e) centent can be reduced, there is higher productivity of propylene and Propylene Selectivity, and coke yield is lower.
Embodiment
In gasoline conversion method provided by the invention, described ordered structure catalyst comprises the composition grain of molecular sieve, silica binder, vanadium matrix and alkaline-earth metal matrix by being formed, then described composition grain grinding is formed the method preparation of coating slurry and coating honeycomb substrate.
Preferably, described ordered structure catalyst preparation method comprises:
(1) molecular sieve, vanadium component, alkaline earth metal component are mixed with water, grinding, obtains the mix slurry that particle diameter d90 is 1-10 micron; With V
2o
5meter vanadium component with in the weight ratio of the molecular sieve of butt for 0.1-35: 100, the mol ratio of vanadium and alkaline-earth metal is 10: 1-1: 60;
(2) slurries step (1) obtained, silica binder component mix, and add or do not add dispersion agent, obtaining coating slurry; Wherein said silica binder component is that particle dia is less than the silicon oxide of 100nm and/or particle dia is less than the precursor species that 100nm can form silicon oxide; The content of described coating slurry Middle molecule sieve is 3-60 % by weight, and silica binder component is (with SiO
2meter) be 0.1-30: 100 with the weight ratio of molecular sieve (in butt), the weight ratio of dispersion agent and molecular sieve (in butt) is 0-20: 100; Described dispersion agent be selected from molecule in the compound having poly-hydroxy, poly carboxylic acid base or polyoxyethylene groups one or more;
(3) with the coating slurry coating honeycomb substrate that step (2) obtains.
The activated coating of the ordered structure catalyst that the method obtains is firm, difficult drop-off in use procedure, and good catalyst activity has higher propene yield and falls sulphur effect.
In the preparation process (1) of described ordered structure catalyst, molecular sieve, vanadium component, alkaline earth metal component and water are mixed, then grinding obtains mix slurry, described grinding can adopt any existing method, such as wet ball grinding can be adopted, described grinding makes the d90 of particle diameter in slurries be 1-10 micron, have higher reactive behavior to make described ordered structure catalyst and have good stability, the d90 of described compound particles diameter is preferably 4-8 micron.The measuring method of described particle diameter can adopt laser particle analyzer method, see ASTM D4464-00 (2005).Wherein said particle diameter d90 is the D90 value of particle size distribution, its implication: the sieve particle volume that in slurries, diameter is less than this value (d90) accounts for 90% of slurries Middle molecule sieve particle overall volume.Described water is deionized water, decationized Y sieve water or distilled water.
Described molecular sieve, vanadium component, alkaline earth metal component to be mixed with water, grinding, by molecular sieve, be added to the water respectively containing the material of vanadium, the material of alkaline including earth metal, then can grind; Also by molecular sieve, be added to the water containing the material of vanadium and alkaline-earth metal, then can grind; Under preferable case, by containing the compound of vanadium, the compound of alkaline including earth metal, in 600-900 DEG C of roasting, to be formed after the composite oxides containing vanadium and alkaline-earth metal again with molecular sieve, water mixed grinding.Wherein, the temperature of described roasting is preferably 750-850 DEG C.The time of roasting is 0.5-100 hour, preferred 1-10 hour.
One or more in the mineral compound of the described material such as vanadium containing vanadium or organic compound, be such as Vanadium Pentoxide in FLAKES, ammonium meta-vanadate, containing one or more in the composite oxides of vanadium and alkaline-earth metal.With the butt weight of activated coating slurries for benchmark, the consumption of vanadium component makes to contain with V in obtained activated coating
2o
5the content of the vanadium component of meter is 0.1-25 % by weight, is preferably 0.2-10 % by weight, is more preferably 2-9 % by weight.
Described alkaline-earth metal be selected from beryllium, magnesium, calcium, strontium, barium one or more, be 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 muriate of the material such as alkaline-earth metal of described alkaline including earth metal, nitrate, vitriol, organic acid salt, containing one or more in the composite oxides of vanadium and alkaline-earth metal, be wherein preferably nitrate or muriate, containing one or more in the composite oxides of vanadium and alkaline-earth metal.
Molecular sieve of the present invention 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 y-type zeolite, rare earth Y type zeolite (REY), baked rare earth Y type zeolite (CREY), ultrastable Y－type zeolite (USY), L zeolite, Beta zeolite, mordenite and ZSM-18 zeolite one or more, be preferably in y-type zeolite and Beta zeolite one or more, one or more in described y-type zeolite such as HY type zeolite, rare earth Y type zeolite, baked rare earth Y type zeolite, ultrastable Y－type zeolite.Described mesopore zeolite refers to the zeolite of its cavernous structure opening in 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, MCM-56 zeolite one or more, preferred ZSM-5 zeolite.Described non-zeolite molecular sieve be selected from there is Different Silicon aluminum ratio silicate (as metal silicate metallosilicate, titanosilicate titanosilicate), metal aluminate metalloaluminates (as germanium aluminate germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metalloaluminophosphate metalloaluminophosphates, aluminosilicophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO) of melts combine, silico-aluminate silicoaluminophosphates (SAPO), one or more in gallium germanate (gallogermanates), be preferably 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, such as, be ZRP zeolite and/or ZSP zeolite.
Step preferably adds dispersion agent in (2), and the weight ratio of dispersion agent and molecular sieve is 0.01-20: 100.By any existing method by mix slurry, silica binder component (silicon oxide and/or the precursor species of silicon oxide can be formed) and dispersant solution mixing, preferred method is: in the mix slurry that step (1) obtains, add silicon oxide and/or can form the precursor species of silicon oxide, stir, preferred churning time is at least 5 minutes, preferred churning time is 15-120 minute, then add dispersant solution to stir, 10-60 minute is stirred after preferably adding dispersant solution, the precursor species that can form silicon oxide can be selected from silicon sol, one or more in water glass.Wherein in dispersant solution, the content of dispersion agent is 1-10 % by weight.Described silica binder component is that particle dia is less than the silicon oxide of 100nm and/or can forms the precursor species of silicon oxide, and preferably, the particle dia of described silica binder component is 1-60nm, and median size (diameter) is preferably 5-30nm; The silicon oxide that described particle dia is less than 100nm is all less than 100nm with the particle dia of the precursor species that can form silicon oxide, is preferably 1-60nm, is more preferably 5-30nm.The described precursor species forming silicon oxide is one or more in silicon sol, water glass or Silica hydrogel.The measuring method of silica binder component size distribution of the present invention can adopt ASTM E2490, i.e. light correlation spectroscopy (PCS).
In step (2), preferably add aqueous dispersant, described dispersant solution add the 0.01-20 % by weight that weight is molecular sieve butt weight, more preferably add-on is the 0.05-18 % by weight of molecular sieve butt weight; Wherein in dispersant solution, the weight percentage of dispersion agent is 1-10 % by weight.Described dispersant solution is prepared by following methods: using dispersion agent as 1 weight part, adds 9-99 parts by weight of deionized water and dispersion agent is dissolved, and the weight percentage obtaining dispersion agent is the dispersant solution of 1-10 % by weight.Described dispersion agent be selected to have in the compound of poly-hydroxy or polyoxyethylene groups active group in all more stable molecule of bronsted lowry acids and bases bronsted lowry one or more, be such as one or more in polyol type, polyoxyethylene-type or poly carboxylic acid radical-type compound, preferably, described dispersion agent is one or more in polyoxyethylene glycol, glycerol, polyvinyl alcohol or polyacrylic acid.
The coating slurry that step (2) obtains comprises molecular sieve, vanadium component, alkaline earth metal component silica binder component, dispersant solution and water, the consumption of each component makes in the slurries obtained, with the gross weight of coating slurry for benchmark, molecular sieve content (in butt) is 3-60 % by weight, be preferably 5-55 % by weight, silica binder component is (with SiO
2meter) be 0.1-30: 100 with the weight ratio of molecular sieve (in butt), be preferably 0.3-25: 100, be more preferably 5-25: 100; The weight ratio of dispersion agent and molecular sieve is 0.01-20: 100, is preferably 0.05-18: 100.With V
2o
5the vanadium component of meter and the weight ratio of molecular sieve are 0.1-35: 100, are preferably 1-15: 100, are more preferably 2-10: 100; The mol ratio of described vanadium and alkaline-earth metal is 4: 1-1: 40.The solid content of described coating slurry, preferably more than 60 % by weight, is more preferably 4-60 % by weight.
In ordered structure catalyst preparation process of the present invention, coating honeycomb substrate described in step (3), can carry out according to existing method, generally include and coating slurry is contacted with honeycomb substrate, described coating slurry is made to be full of all ducts of honeycomb substrate, then carrier outer surface is blown off with pressurized air, dry, the step of roasting.Described honeycomb substrate can select commercially available composite oxides honeycomb substrate such as cordierite carrier also can select the honeycomb substrate of other material.Described pressurized air blows off the method for carrier outer surface, can according to existing method, such as method disclosed in CN1191127C.Described drying can adopt the mode of oven dry, such as, at 100-120 DEG C, dry 2-5 hour, the preferred 600-700 DEG C of temperature of described roasting, the preferred 1-3 hour of roasting time.Obtain the ordered structure catalyst containing combination of molecular sieve activated coating and honeycomb substrate after roasting, wherein said activated 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.
Ordered structure catalyst of the present invention, with the weight of catalyzer for benchmark, is made up of the honeycomb substrate of 60-99.9 % by weight and the activated coating of 0.1-40 % by weight; Preferred activated coating accounts for 2-35 % by weight, and honeycomb substrate accounts for 65-98 % by weight.Described activated coating comprise 65-99 % by weight molecular sieve, with V
2o
5count the vanadium matrix of 0.1-25 % by weight, with the alkaline-earth metal matrix of oxide basis 0.1-25 % by weight with SiO
2meter 0.1-30 % by weight silica binder; Preferably, described coating comprises the silica binder of 0.3-20 % by weight and molecular sieve, the vanadium matrix of 0.2-10 % by weight, the alkaline-earth metal matrix of 0.1-20 % by weight of 70-95 % by weight; More preferably the molecular sieve of 75-90 % by weight, the silica binder of 2-18 % by weight, the V of 2-10 % by weight is comprised
2o
5with the alkaline-earth metal of 0.5-20 % by weight.The coat-thickness of described catalyzer can be selected as required, and such as its thickness can be 1nm-1mm, is usually no more than 500 μm, is preferably 1-500 μm.
Preferably also introduce other metal component in the activated coating slurries of ordered structure catalyst provided by the invention, this other metal component is one or more in IIIA race metal, IVA race metal, IIB race metal, IVB race metal, the metal of VB race except vanadium, group vib metal, group VIII metal and rare earth compound.Described other metal be preferably in gallium, indium, thallium, germanium, tin, zinc, cadmium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, iron, cobalt, nickel, lanthanide rare metal one or more, described lanthanide rare metal finger lanthanum, cerium, lanthanum rich norium or rich cerium misch metal.Other described inorganic oxide matrix was introduced before described silica binder component, under preferable case, described other metal component and vanadium and alkaline-earth metal are incorporated in described coating slurry after being mixed to form the composite oxides containing vanadium and alkaline-earth metal.With the butt weight of catalyst activity coating for benchmark, with oxide basis, the introduction volume of described other metal component makes the content of the metal matrix being derived from described other metal component in the activated coating obtained be 0-20 % by weight, and the content of described other metal matrix is preferably 0.5-10 % by weight.
Also other inorganic oxide matrix can be contained in the activated coating of ordered structure catalyst provided by the invention, with the butt weight of activated coating for benchmark, with the content of other inorganic oxide matrix described in oxide basis for 0-30 % by weight, preferably more than 25 % by weight, more preferably no more than 10 % by weight.Other inorganic oxide matrix described be selected from aluminum oxide, silicon oxide, amorphous aluminum silicide and clay one or more.The d90 of described inorganic oxide matrix is 1-10 micron, is preferably 4-8 micron.Described inorganic oxide matrix and the weight ratio of molecular sieve are 0-60: 100, are preferably 0-40: 100.Described clay can be selected from kaolin, halloysite, polynite, diatomite, tired de-soil one or more, preferred kaolin.One or more in described alumina host such as gama-alumina, η-aluminum oxide, κ aluminum oxide, described silica binder such as silochrom.When preparing coating slurry in such cases, described electrodeless matrix of oxide is introduced in step (1) or (2), preferably introduced before dispersion agent, more preferably added before silica binder component, be incorporated in described coating slurry after more described inorganic oxide and vanadium and alkaline-earth metal being mixed to form the composite oxides containing vanadium and alkaline-earth metal.
Of the present invention containing alkene and sulfur oil such as catalytically cracked gasoline.Described can be 50-2000ppm containing sulphur content in alkene and sulfur oil, and be generally 150-1500ppm, be particularly useful for sulfur-bearing and olefin gasolines that sulphur content is not less than 250ppm, its olefin(e) centent can be 20-70 % by weight, is generally 25-60 % by weight.
Embodiment 1
(1) by 108 grams of HY type molecular sieve (in butt) powder (d90=14 micron, technical grade, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product) and 3.86 grams of ammonium meta-vanadate (NH
4vO
3, chemical pure, Beijing Chemical Plant produce), 55.5 grams of anhydrous nitric acid magnesium (Mg (NO
3)
2, chemical pure, Beijing Chemical Plant produce) and 834.2 grams of deionized waters mix, wet ball grinding becomes slurries, compound particles diameter d 90=5 micron;
(2) 180 grams of water glass (silicon oxide-containing 15 % by weight is added in the slurries obtained in step (1), catalyzer asphalt in Shenli Refinery of China Petrochemical Industry produces, modulus is 3.2, particle dia is 1-5nm, median size is 3nm), in the add-on of silicon oxide water glass is HY molecular sieve 25 % by weight, stir 10 minutes, add polyglycol solution 3.24 grams (in solution, the weight percentage of polyoxyethylene glycol is 2 % by weight), the add-on of this solution is 3 % by weight of molecular sieve, stir and within 20 minutes, obtain catalyst coat and prepare mix slurry (coating slurry).
Mix slurry coating honeycomb substrate (cordierite honeycomb carrier is prepared with obtained catalyst coat, 31 holes/square centimeter, non-metal chemical mechinery works of Jiangsu honeycomb pottery subsidiary factory product) all inner surfaces of pores, with pressurized air, (pressure is 0.4MPa, lower same) blow off honeycomb substrate outside surface, dry 2 hours at 120 DEG C, roasting 1 hour at 650 DEG C, obtain the ordered structure catalyst C1 with activated coating, its coating levels is 5.5%.In Table 1-1.
Embodiment 2
(1) 11 grams of ammonium meta-vanadates (specification is with embodiment 1), 13.9 grams of anhydrous nitric acid magnesium (specification is with embodiment 1) are mixed, by the solid mixture that obtains 800 DEG C of roastings 2 hours, obtain the composite oxides VA1 containing vanadium and alkaline-earth metal.The composition of VA1 is listed in table 1-1;
(2) composite oxides VA1 and the 120 gram rare earth Y type molecular sieve (in butt, lower same) powder (d90=12 micron, the RE that (1) are obtained
2o
3content 3 % by weight, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product) and 252 grams of deionized water mixing, wet ball grinding becomes slurries, the particle diameter d90=8 micron of slurries;
(3) 30 grams of silicon sol (silicon oxide-containing 20 % by weight is added in the slurries obtained in (2), catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, the particle dia of silicon sol is 12-35nm, median size is 20nm), the silicon oxide amount introduced by silicon sol is 5 % by weight of molecular sieve, stirs 60 minutes; Add polyoxyethylene glycol and polyacrylic acid mixing solutions 21.6 grams (polyethyleneglycol content is 3 % by weight, and polyacrylic acid content is 5 % by weight), solution add-on is 18 % by weight of molecular sieve, stirs and obtains 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), carrier outer surface is blown off with pressurized air, dry 2.5 hours at 120 DEG C, roasting 2.5 hours at 650 DEG C, obtains the ordered structure catalyst C2 with molecular sieve catalyst coating.Coating levels is 7.6%, and thickness is 89 microns.
Embodiment 3-4
(1) composite oxides of vanadium and alkaline-earth metal are contained by the method preparation of (1) in embodiment 2, unlike replacing anhydrous nitric acid magnesium with 23.2 grams of anhydrous nitric acid calcium or with the mixture of 23.9 grams of anhydrous nitric acid magnesium and 7.8 grams of anhydrous nitric acid calcium respectively, composite oxides VA2 and VA3 of vanadium component and alkaline earth metal component must be contained.The composition of VA2-VA3 is listed in table 1-1.
(2) by the method prepared slarry of (2) in embodiment 2, unlike replacing VA1 with VA2 and VA3 respectively, (lattice constant is 24.35 dusts to use overstable gamma zeolite respectively, sodium oxide is 0.5 % by weight, 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, silica alumina ratio is 30, and Zhou village catalyst plant is produced) replace rare earth exchanged Y zeolite.
(3) by the method Kaolinite Preparation of Catalyst of (3) in embodiment 2, unlike adding polyacrylic acid solution 12 grams (polyacrylic acid content is 1 % by weight) in slurries, polyacrylic acid solution add-on is 10 % by weight of molecular sieve, stir 30 minutes, obtain catalyst coat slurries.Gained catalyst coat slurries are full of all ducts of honeycomb substrate (described honeycomb substrate is with embodiment 1), carrier outer surface is blown off with pressurized air, dry 2.5 hours at 120 DEG C, at 650 DEG C, roasting 2.5 hours, obtains ordered structure catalyst C3-C4.
Embodiment 5-10
The following examples illustrate Catalysts and its preparation method provided by the invention.
(1) contain the composite oxides of vanadium and alkaline earth metal component by the method preparation of (1) in embodiment 2, difference is respectively:
1), in the mixture of ammonium meta-vanadate, anhydrous nitric acid magnesium, the anhydrous nitric acid zinc (chemical pure, Beijing Chemical Plant produces) of 5.9 grams is also added.
2), in the mixture of ammonium meta-vanadate, anhydrous nitric acid magnesium, also add the suspension liquid 62.7 grams of rare-earth hydroxide, containing rare earth oxide 25 % by weight in this suspension liquid, wherein lanthanum trioxide 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 liquid is (RE in 42.6 grams of rare earth chlorides (Gansu Rare Earth Co.'s product) aqueous solution
2o
3concentration 36.73 % by weight) add 2.1 kilograms of strong aquas (concentration 17 % by weight), make rare earth ion precipitate the suspension liquid formed; Ammonium meta-vanadate (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 meta-vanadate, anhydrous nitric acid magnesium, zirconium oxychloride (the Jiangxi Jing An Chemical Co., Ltd. product) aqueous solution 28.2 milliliters and 3.14 grams of Calcium Chloride Powder Anhydrouss that concentration is 2.0 mol/L is also added.
4) in the mixture of ammonium meta-vanadate, anhydrous nitric acid magnesium, iron(ic) chloride (chemical pure, the Beijing Chemical Plant produces) aqueous solution 34.4 milliliters that concentration is 2.0 mol/L is also added; Ammonium meta-vanadate (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 meta-vanadate, anhydrous nitric acid magnesium, gallium chloride (chemical pure is produced) aqueous solution 31.3 milliliters that concentration is 2 mol/L is also added.
6), in the mixture of ammonium meta-vanadate, anhydrous nitric acid magnesium, kaolin (butt) 4.8 grams is also added.
Obtain the composite oxides VA4 containing vanadium and alkaline-earth metal, VA5, VA6, VA7, VA8, VA9.The composition of VA4-VA9 is listed in table 1-2.
(2) by the method Kaolinite Preparation of Catalyst of embodiment 2, unlike using VA4 respectively, VA5, VA6, VA7, VA8, VA9 replace VA1, obtain ordered structure catalyst C5-C10.
Embodiment 11
By the method Kaolinite Preparation of Catalyst of embodiment 2, be not both and replace rare earth Y type molecular sieve by 180 grams of HZSM-5 type molecular sieve powder (silica alumina ratio is 60 for d90=14 micron, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product), wet ball grinding becomes slurries, particle diameter d90=5 micron in slurries; 45 grams of silicon sol (silicon oxide-containing 20 % by weight is added in slurries, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, the particle dia of silicon sol is 12-35nm, and median size is 20nm), the silicon oxide amount introduced by silicon sol is 5 % by weight of molecular sieve, stirs 60 minutes; (polyethyleneglycol content is 3 % by weight to add polyoxyethylene glycol and polyacrylic acid mixing solutions 32.4 grams, polyacrylic acid content is 5 % by weight), solution add-on is 18 % by weight of molecular sieve, stirs within 30 minutes, to obtain catalyst coat and prepare mix slurry.Prepare mix slurry coating honeycomb substrate with obtained catalyst coat to obtain (at 120 DEG C dry 1.5 hours, roasting 2 hours at 650 DEG C) and obtain ordered structure catalyst C11.Coating levels 40.02%.
Embodiment 12
By the method Kaolinite Preparation of Catalyst of embodiment 2, unlike with 100 grams of DASY0.0 type molecular sieve powder (d90=14 microns, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product) and 50 grams of beta molecular sieve powder (d90=14 microns, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product) replace rare earth Y type molecular sieve, wet ball grinding becomes slurries, the particle diameter d90=5 micron in slurries; Then 80 grams of Silica hydrogel (silicon oxide-containing 15 % by weight is added, Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery product, the viscosity of Silica hydrogel is 600cst (25 DEG C), granularity is 5-15 nanometer, median size is 12nm), silicon oxide add-on is 12 % by weight of molecular sieve, stir 30 minutes, add 22.5 grams of glycerin solution (glycerol weight percentage is 6 % by weight), glycerin solution add-on is 15 % by weight of molecular sieve, stirs and obtains catalyst coat slurries in 10 minutes.Catalyst coat slurries are full of all ducts of honeycomb substrate, blow off carrier outer surface with pressurized air, dry 3 hours at 120 DEG C, at 650 DEG C, roasting 1 hour, obtains ordered structure catalyst C12.Coating levels 3.6%.
Embodiment 13
By the method Kaolinite Preparation of Catalyst of embodiment 2, rare earth Y type molecular sieve is replaced unlike by 160 grams of SAPO-11 molecular sieve powder (d90=14 micron, technical grade, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product), wet ball grinding becomes slurries, particle diameter d90=5 micron, then 50 grams of silicon sol (silicon oxide-containing 22 % by weight is added wherein, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, silica sol particle diameter is 5-15nm, median size is 10nm) and 44 grams of Silica hydrogel (silicon oxide-containings 15 % by weight, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, the viscosity of Silica hydrogel is 600cst (25 DEG C), particle dia scope is 5-15 nanometer, median size is 12nm), silicon oxide add-on is 11 % by weight of molecular sieve, stir 30 minutes, add polyvinyl alcohol solution 19.2 grams (polyvinyl alcohol weight percentage ratio is 1 % by weight), add-on is 12 % by weight of molecular sieve, stir and obtain catalyst coat slurries in 20 minutes.Obtained coating solution is full of all ducts of honeycomb substrate, blows off carrier outer surface with pressurized air, dry 2 hours at 120 DEG C, at 650 DEG C, roasting 1.5 hours, obtains ordered structure catalyst C13.Coating levels 17.9%.
Embodiment 14
By the method Kaolinite Preparation of Catalyst of embodiment 2, unlike with 180 grams of HZSM-5 type molecular sieve powder (d90=14 microns, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product), silica alumina ratio is that 60 replacement rare earth Y type molecular sieve wet ball grindings become slurries, particle diameter d90=5 micron in slurries; Add polyoxyethylene glycol and polyacrylic acid mixing solutions 32.4 grams (polyoxyethylene glycol and polyacrylic acid weight percentage are divided into 3 % by weight and 5 % by weight), add-on is 18 % by weight of molecular sieve, stir 30 minutes, then 45 grams of silicon sol (silicon oxide-containing 20 % by weight is added, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, silica sol particle diameter is 12-35nm, median size is 20nm), silicon oxide add-on is 5 % by weight of molecular sieve, stir 60 minutes, obtain catalyst coat slurries.Catalyst coat slurries are full of all ducts of honeycomb substrate, blow off carrier outer surface with pressurized air, dry 1.5 hours at 120 DEG C, roasting 2 hours at 650 DEG C.Obtain ordered structure catalyst C14.Coating levels 8.3%.
Table 1-1
Table 1-2
Wherein said deflation: be the duct 5 minutes that the ordered structure catalyst obtained is swept in 10 meter per second normal temperature (25 DEG C) air wind with flow velocity, then be 10 meter per seconds with flow velocity, temperature is weigh in the duct of the ordered structure catalyst that the warm air blowoff of 400 DEG C obtains for 5 minutes, obtains the weight of ordered structure catalyst after warm air blowoff.(catalyst weight before the catalyst weight/deflation after 1-deflation) × 100%, is designated as deflation loss amount.
Embodiment 15-28
Embodiment 15-28 illustrates the effect of regular catalyst provided by the invention for steam cracking.
The ordered structure catalyst provided in embodiment 1-14 is seated in tubular reactor, then be 37.6 % by weight by olefin(e) centent, sulphur content is contact in the reactor with ordered structure catalyst after the olefine contained gasoline of 628 μ g/g is preheating to 250 DEG C, inject the water vapor of 250 DEG C of preheatings, the weight hourly space velocity keeping stock oil to inject is 20 hours simultaneously
-1, water/oily feed weight ratio is 0.05, and temperature of reaction is 620 DEG C, and pressure is 0.05MPa (gauge pressure), continuously feeding 2.0 hours, products therefrom sampling is analyzed.Reaction result is in table 2.
Embodiment 29
(1) by 108 grams of (in butt, lower same) HY type molecular sieve powder (d90=14 micron, technical grade, catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product) and 3.86 grams of ammonium meta-vanadate (NH
4vO
3, chemical pure, Beijing Chemical Plant produce), 55.5 grams of anhydrous nitric acid magnesium (Mg (NO
3)
2, chemical pure, Beijing Chemical Plant produce) and 834.2 grams of deionized waters mix;
(2) 180 grams of water glass (silicon oxide-containing 15 % by weight is added in the slurries obtained in step (1), catalyzer asphalt in Shenli Refinery of China Petrochemical Industry produces, modulus is 3.2, particle dia is 1-5nm, median size is 3nm), in the add-on of silicon oxide water glass is molecular sieve 25 % by weight, stir and obtain mix slurry in 30 minutes; This mix slurry spraying dry is obtained microballoon, thus obtained microsphere was in 600 DEG C of roastings 2 hours, then mix with 950 grams of water and pull an oar, wet ball grinding, obtain the slurries that particle diameter d90 is 5 microns, add polyglycol solution 3.24 grams (in solution, the weight percentage of polyoxyethylene glycol is 2 % by weight) wherein, then obtain catalyzer D1 according to the method coating honeycomb substrate of embodiment 1.Its deflation loss amount is 21.5%.
Embodiment 30
According to the method for embodiment 15, D1 catalyzer is evaluated, the results are shown in Table 2.
Comparative example 1
According to the method Kaolinite Preparation of Catalyst D2 of embodiment 29, vanadium and alkaline-earth metal is not contained unlike in catalyzer, then according to the method evaluation of embodiment 15, its reaction result: in product gasoline, sulphur content is 552 μ g/g, coke is 0.21 gram, propene yield is 20.13 % by weight, Propylene Selectivity 39.7 % by weight.
Table 2
Table 2 (Continued)
From table 2, adopt method provided by the invention, steam cracking reaction conversion is carried out to the gasoline containing alkene and sulfide, the olefin(e) centent in gasoline and sulphur content not only can be made to reduce, liquid phase sulphur transformation efficiency improves, also there is higher Propylene Selectivity and productivity of propylene, and coke yield is lower.
Claims (14)
1. one kind reduce sulfur in gasoline and olefin(e) centent and prepare propylene containing alkene and sulfur oil method for transformation, comprising will containing alkene and sulfur oil and ordered structure catalyst contact reacts, wherein, described ordered structure catalyst is made up of honeycomb substrate and activated coating, described activated coating comprises molecular sieve, vanadium matrix, alkaline-earth metal matrix and silica binder, the mol ratio of vanadium and alkaline-earth metal is 10: 1-1: 60, one or more in large pore zeolite, mesopore zeolite and non-zeolite molecular sieve of described molecular screening; Described alkaline-earth metal is one or more in beryllium, magnesium, calcium, strontium, barium and radium;
Described ordered structure catalyst is obtained by the method comprised the following steps:
(1) molecular sieve, vanadium component, alkaline earth metal component are mixed with water, grinding, obtain the mix slurry that particle diameter d90 is 4-8 micron, the mol ratio of vanadium and alkaline-earth metal is 10: 1-1: 60, with V
2o
5meter vanadium component with in the weight ratio of the molecular sieve of butt for 0.1-35: 100;
(2) slurries step (1) obtained, silica binder component mix, and add dispersion agent, obtain coating slurry; Wherein said silica binder component is that particle dia is less than the silicon oxide of 100nm and/or particle dia is less than the precursor species that 100nm can form silicon oxide; The content of described coating slurry Middle molecule sieve is 3-60 % by weight, with SiO
2meter silica binder component with in the weight ratio of the molecular sieve of butt for 0.3-30: 100, the weight ratio of dispersion agent and molecular sieve is 0.1-20: 100; Described dispersion agent be selected from molecule in the compound having poly-hydroxy, poly carboxylic acid base or polyoxyethylene groups one or more;
(3) with the coating slurry coating honeycomb substrate that step (2) obtains.
2. according to claim 1 containing alkene and sulfur oil method for transformation, it is characterized in that, described activated coating comprises the molecular sieve of 65-99 % by weight, with V
2o
5count 0.1-25 % by weight vanadium matrix, with oxide basis 0.1-20 % by weight alkaline-earth metal with SiO
2meter 0.1-30 % by weight silica binder.
3. according to claim 1 containing alkene and sulfur oil method for transformation, it is characterized in that, described catalytic condition comprises: the temperature of reaction is 400-650 DEG C, and weight hourly space velocity is 1-1000h
-1, steam and the described weight ratio containing alkene and sulfur oil are 0.02-3: 1.
4. according to claim 1 containing alkene and sulfur oil method for transformation, it is characterized in that, with V
2o
5meter vanadium component with in the weight ratio of the molecular sieve of butt for 0.2-15: 100, with SiO
2meter silica binder component with in the weight ratio of the molecular sieve of butt for 0.3-25: 100.
5. according to claim 1 containing alkene and sulfur oil method for transformation, it is characterized in that, the mol ratio of described vanadium and alkaline-earth metal is 4: 1-1: 40.
6. according to any one of claim 1,2,4 or 5 containing alkene and sulfur oil method for transformation, it is characterized in that, the content of described molecular sieve is 70-95 % by weight.
7. according to claim 1 containing alkene and sulfur oil method for transformation, it is characterized in that, one or more in y-type zeolite, Beta zeolite and ZSM-5 zeolite of described molecular screening.
8. according to claim 1 containing alkene and sulfur oil method for transformation, it is characterized in that, described silica binder component is one or more in silicon sol, water glass or Silica hydrogel.
9. according to claim 1 or 8 containing alkene and sulfur oil method for transformation, it is characterized in that, the particle dia of described silica binder component is 1-60nm, median size 5-30nm.
10. according to claim 1 containing alkene and sulfur oil method for transformation, it is characterized in that, add silicon oxide in the slurries obtained in step (1) in the preparation process (2) of described ordered structure catalyst and/or the precursor species of silicon oxide can be formed, stir, then add dispersant solution, stir.
11. according to claim 1 or 10 containing alkene and sulfur oil method for transformation, it is characterized in that, step adds dispersant solution in (2), and in dispersant solution, the concentration of dispersion agent is 0.1-10 % by weight; The weight ratio of dispersant solution and molecular sieve is 0.1-20: 100.
12. according to claim 1 or 10 or 11 containing alkene and sulfur oil method for transformation, it is characterized in that, described dispersion agent be selected from polyoxyethylene glycol, glycerol, polyvinyl alcohol or polyacrylic acid one or more.
13. is according to claim 1 containing alkene and sulfur oil method for transformation, it is characterized in that, described vanadium component is Vanadium Pentoxide in FLAKES, ammonium vanadate or containing one or more in the composite oxides of vanadium and alkaline-earth metal; Described alkaline earth metal component is the muriate of alkaline-earth metal, nitrate, vitriol, organic acid salt and containing one or more in the composite oxides of vanadium and alkaline-earth metal.
14. is according to claim 11 containing alkene and sulfur oil method for transformation, and it is characterized in that, the activated coating of this catalyzer contains inorganic oxide matrix and/or other metal matrix; Described other metal is one or more in IIIA race metal, IVA race metal, IIB race metal, IVB race metal, the metal of VB race except vanadium, group vib metal, group VIII metal and rare earth metal, with the weight of catalyst activity coating for benchmark, with oxide basis, the content of metal matrix other in described activated coating is 0-20 % by weight, with the content of inorganic oxide matrix described in oxide basis for 0-30 % by weight.
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