CN101147874A - Catalyst for preparing propylene and ethylene by C4 olefins and preparation method - Google Patents
Catalyst for preparing propylene and ethylene by C4 olefins and preparation method Download PDFInfo
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- CN101147874A CN101147874A CNA2007101346990A CN200710134699A CN101147874A CN 101147874 A CN101147874 A CN 101147874A CN A2007101346990 A CNA2007101346990 A CN A2007101346990A CN 200710134699 A CN200710134699 A CN 200710134699A CN 101147874 A CN101147874 A CN 101147874A
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Abstract
The present invention relates to a catalyst for preparing propylene and ethylene by using C4-olefine and its preparation method. Under the condition of high-temperature and low-pressure it has high conversion rate of C4-olefine, high propylene yield and high ethylene yield. Said catalyst composition includes the following components: (by molecular sieve weight) 0.1-15wt% of transition element metal as adjuvant, 0.01-10wt% of alkaline earth metal, 0.01-10wt% of non-metal phosphours, 0.01-10wt% of rare earth metal, 2-60wt% of inorganic oxide adhesive and the rest is molecular sieve as main active component.
Description
Technical field
The present invention relates to catalyst and preparation method that a kind of preparing propylene from C 4 olefins and ethene are used, be applicable to catalytic reaction, belong to the catalyst preparation technology of Industrial Catalysis technical field.
Background technology
Propylene and ethene are important basic Organic Chemicals, are mainly used in chemical products such as producing polypropylene, polyethylene, polyacrylonitrile.In recent years, the driving that increased fast by downstream propylene and ethene derivatives product demand, the consumption figure of propylene and ethene significantly improves.Propylene particularly, traditional ethene coproduction and refinery reclaim cyclopropene method and have been difficult to satisfy the demands, and therefore, the catalysis technique of exploitation propylene enhancing has very important significance.Petroleum chemical enterprise's richness is produced C 4 olefin at present, there are a considerable amount of C 4 olefins to be used as low value-added products such as liquefied gas as fuel in the world wide, therefore, by C 4 olefin propylene enhancing and ethene, can utilize the C 4 olefin resource a considerable number of, that added value is lower on the one hand, can obtain propylene of many uses, that added value is high and ethylene product again on the other hand, and the key problem in technology of realizing volume increase is to develop to produce the new catalyst that propylene and ethene are used.At present, utilize C 4 olefin catalysis system propylene to mainly contain cracking and disproportionation processes, and C 4 olefin disproportionation system propylene generally all will consume the ethene of some, and domestic ethene resource is less.Opposite C 4 olefin cracking system propylene technology then when producing propylene, also can obtain a certain amount of ethene, has very big attraction from investment cost and production cost, has the stronger market competitiveness.
CN1274342A has reported that openly adopting with the ZSM-5 molecular sieve is carrier, and by ion-exchange carrying alkali metal, IB family metallic catalyst catalytic mixing preparing propylene from C 4 olefins and ethene, its propylene and yield of ethene are respectively 34% and 10%; CN1712496A has openly reported by the silicoaluminophosphate SAPO of ultra-fineization of magnesium, molybdenum or Zirconium oxide modification series molecular sieve catalyst catalytic reaction thing (in the hydrocarbon mixture of naphtha, diesel oil and carbon containing four～carbon eight alkene at least a) system propylene and ethene, its propene yield is 27.3%, and yield of ethene is 40.3%; Openly with the ZSM-5 catalyst cracking c_4 alkene system propylene of 5～100% steam treatment, its propene yield is 29% to WO9929805, does not relate to ethene.The EP0109059 patent report be used for carbon four～carbon laurylene hydrocarbon is converted into the ZSM-5 or the ZSM-11 catalyst preparation process of propylene and ethene, its olefin conversion is 88.6%, the selectivity of propylene is 38.5%, selectivity of ethylene is 7.4%; US6307117 discloses the method for a kind of carbon four and carbon four above alkene system propylene, adopt load silver or IB family metal, almost do not have a ZSM-5 molecular sieve catalyst of Bronsted acid, possesses anti-preferably carbon deposit performance, its propene yield is 27.9%, yield of ethene is 12.7%, and CN1317543A then discloses and added copper or the silver-colored yield that can improve ethene.The catalyst that US6586649 discloses is Cs-P-WO
3/ SiO
2, be auxiliary agent with phosphate, borate or magnesia etc., its propylene and yield of ethene can reach 35% and 8% respectively.The ZSM-5 molecular sieve has unique pore passage structure, good " shape selective catalysis " ability as the solid acid catalyst for cracking, can suppress the carbon deposit of product molecule in molecular sieve pore passage effectively, help improving the selectivity and the stability of catalytic reaction, wherein the existence of the acid amount in the catalyst, acids type is of crucial importance to cracking reaction.Therefore, the ZSM-5 catalyst is carried out a series of study on the modification, the acidity energy of appropriate regulation catalyst surface can suppress the carbon deposit in catalyst for cracking surface and ZSM-5 molecular sieve aperture.Rare earth elemental metals is widely used in all kinds of catalytic reactions simultaneously, mainly based on its unique electronic structure and excellent anti-carbon performance.Therefore, exploitation ZSM-5 modified catalyst adds rare earth elemental metals, can obtain all higher and reproducible preparing propylene from C 4 olefins of activity, selectivity, stability and ethene catalyst.At present, the type catalyst still is in conceptual phase, does not see industrialized application report.
Summary of the invention
Technical problem: the purpose of this invention is to provide catalyst and preparation method that a kind of preparing propylene from C 4 olefins and ethene are used, this catalyst is under the condition of high temperature, low pressure, C 4 olefin can be catalytically conveted to propylene and ethene, have higher C 4 olefin conversion ratio, propene yield and yield of ethene.
Technical scheme: the catalyst that preparing propylene from C 4 olefins of the present invention and ethene are used comprises that with molecular sieve be main active constituent, with the transition elements metal is auxiliary agent, with alkaline-earth metal or nonmetal phosphorus, rare earth elemental metals is modifier, is the binding agent moulding with resistant to elevated temperatures inorganic oxide; Weight with molecular sieve is calculated, the addition of transition elements metal is 0.1～15wt%, the addition of alkaline-earth metal is 0.01～10wt%, the addition of nonmetal phosphorus is 0.01～10wt%, the addition of rare earth elemental metals is 0.01～10wt%, the addition of inorganic oxide binder is 2～60wt%, and all the other are molecular sieve.
Described molecular sieve is one or more mixtures in A type or X type or Y type or ZSM type series or the MCM type series.
Described transition elements metal is the combination of one or several metals in molybdenum, tungsten, the rhenium.
Described alkaline-earth metal is the combination of one or more metals in calcium, magnesium, strontium, the barium.
Described rare earth elemental metals is selected from the combination of one or more metals in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, the europium.
Described inorganic oxide binder is solid or colloidal sol, and wherein solid is one or more the compound in aluminium oxide, silica, imvite, the kaolin; Colloidal sol is one or both the compound in Ludox, the aluminium colloidal sol.
The Preparation of catalysts method that preparing propylene from C 4 olefins and ethene are used is:
Step 1), with molecular sieve and the aqueous solution that contains the aqueous solution of nonmetal phosphorus or alkaline including earth metal at 60～100 ℃ of dipping 2～10h down, be evaporated under 60～100 ℃ dry, 60～180 ℃ of drying 2～12h, 400～700 ℃ of roasting 3～10h, get a modified catalyst after the cooling
Step 2), with the modified catalyst and the aqueous solution that contains rare earth elemental metals, at 60～100 ℃ of dipping 2～10h down, be evaporated under 60～100 ℃ dry, 60～180 ℃ of down dry 2～12h, 400～700 ℃ of roasting 3～10h get twice-modified catalyst after the cooling
Step 3), twice-modified catalyst and a certain amount of extrusion aid are mixed, add inorganic oxide binder furnishing pastel again, spin or extruded moulding behind the mixing; 60～180 ℃ of drying 2～12h, 400～700 ℃ of following roasting 3～10h obtain preformed catalyst after the cooling,
Step 4), with preformed catalyst under 600～900 ℃, be 1: 5～1: 30 by the volume ratio of steam and nitrogen, with steam treatment preformed catalyst 2～40h, calculate with the weight of every gram catalyst, the amount that per hour feeds steam is 1～10mL; After the cooling, handle preformed catalyst 3～6 grams, under 60～100 ℃ of temperature, handle preformed catalyst 1～5h with the aqueous solutions of organic acids of 0.1～5mol/L by every milliliter of aqueous solutions of organic acids; Cooling back suction filtration, 60～180 ℃ of drying 2～12h then, 400～700 ℃ of roasting 3～10h obtain the steam treatment catalyst after the cooling,
Step 5), the steam treatment catalyst is added in the aqueous solution that contains the transition elements metal, and to transfer pH with the inorganic acid of 1～10wt% be 1.0～5.0, flood 2～10h down at 60～100 ℃, be evaporated to dry under 60～100 ℃, 60～180 ℃ of drying 2～12h, 400～700 ℃ of roasting 3～10h obtain catalysts after the cooling
Step 6), with catalysts at 400～600 ℃, logical nitrogen or helium, activation processing 1～5h obtains activating catalyst after the cooling; Activating catalyst can be directly used in the catalytic reaction of C 4 olefin cracking system propylene and ethene.
In step 3), extrusion aid is sesbania powder, polybasic carboxylic acid or the compound of the two, and wherein polybasic carboxylic acid can be one or more the sour mixtures in citric acid, oxalic acid and the tartaric acid, and in the weight of molecular sieve, the addition of extrusion aid is 1～15wt%; Organic acid in the step 4) is one or more the sour mixtures in formic acid, acetate, malonic acid, the butyric acid; Inorganic acid in the step 5) is one or more the sour mixtures in nitric acid, sulfuric acid, the hydrochloric acid.
Beneficial effect: the invention provides catalyst and preparation method that a kind of preparing propylene from C 4 olefins and ethene are used, this catalyst has higher C 4 olefin conversion ratio, propene yield and yield of ethene under the condition of high temperature, low pressure, reaction stability is good, iterative regenerable, and the catalyst reaction better performances after the regeneration.
Characteristics of the present invention are:
(1) be main active constituent with molecular sieve, utilize molecular sieve to have the characteristics of bigger serface, nonmetal phosphorus or alkaline-earth metal, rare earth elemental metals and transition elements metal are disperseed fully on the molecular sieve catalyst surface, improved catalytic reaction activity, utilize the good appearance charcoal ability of molecular sieve simultaneously, improved the stability of catalytic reaction.
(2) Preparation of catalysts adopts infusion process, especially adopts step impregnation method, helps nonmetal phosphorus or alkaline-earth metal, rare earth elemental metals and transition elements metal and is disperseed fully on the molecular sieve surface.Nonmetal phosphorus or alkaline-earth metal can effectively be regulated the structure and the acid energy of main active constituent molecular sieve as catalyst modifier, improve its hydrothermal stability; The adding of rare earth elemental metals can further strengthen the anti-carbon deposition ability of catalyst, improves the stability of catalytic reaction; The interpolation of transition elements metal can further improve the yield of ethene.
(3) Preparation of catalysts adopts the laggard capable steam treatment of first moulding, carry out treatment process with organic acid again, flood the double-steeping technology of modification before the employing shaping of catalyst after dipping modification and the moulding once more, improved the hydrothermal stability of catalyst, made catalyst have higher activity, selectivity, stability and regenerability.
(4) added inorganic oxide binder in the shaping of catalyst process of the present invention, obviously improved the mechanical strength of catalyst, the catalyst mechanical strength height that the present invention makes satisfies the condition of suitability for industrialized production, use fully, and the catalyst preparation process strong operability, good reproducibility.
(5) catalytic reaction of preparing propylene from C 4 olefins of the present invention and ethene adopts fluid bed or fixed bed reactors, preferred fixed bed reactors.Its reaction unit is made up of a preheater and a cracking reactor.Wherein, the serviceability temperature of preheater reactor is 100～500 ℃, preferred 200～350 ℃.What load in the cracking reactor is C 4 olefin cracking activating catalyst, and reaction temperature is 400～700 ℃, preferred 500～600 ℃.Reaction pressure is 0.1MPa, and the mass space velocity of C 4 olefin is 1.0～5.0h
-1, preferred 1.0～3.0h
-1Carrier gas in the course of reaction (nitrogen or helium) is 1: 1～8: 1 with the volume ratio of C 4 olefin.
The specific embodiment
The catalyst that described preparing propylene from C 4 olefins and ethene are used is to be main active constituent with molecular sieve, with the transition elements metal is auxiliary agent, with alkaline-earth metal or nonmetal phosphorus (P), rare earth elemental metals is modifier, is the binding agent moulding with resistant to elevated temperatures inorganic oxide.Weight with molecular sieve is calculated, and the addition of each component is: the addition of transition elements metal is 0.1～15wt%, preferred 1～10wt%; The addition of alkaline-earth metal is 0.01～10wt%, preferred 0.1～3wt%; The addition of nonmetal phosphorus is 0.01～10wt%, preferred 0.5～5wt%; The addition of rare earth elemental metals is 0.01～10wt%, preferred 0.1～5wt%; The addition of inorganic oxide binder is 2～60wt%, preferred 10～50wt%; All the other are molecular sieve.
Molecular sieve in the described catalyst is one or more mixtures in A type or X type or Y type or ZSM type series or the MCM type series, is best with the type ZSM 5 molecular sieve.
Transition elements metal in the described catalyst is the combination of one or several metals in molybdenum (Mo), tungsten (W), the rhenium (Re), is the best with tungsten (W) wherein.Alkaline-earth metal is the combination of one or more metals in magnesium (Mg), calcium (Ca), strontium (Sr) barium (Ba), is good with barium metal (Ba).Rare earth elemental metals is the combination of one or more metals in lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), the europium (Eu), is good with lanthanoid metal (La), cerium (Ce).
Above-mentioned Preparation of catalysts method can adopt co-impregnation or step impregnation method, is good with step impregnation method, can adopt methods such as conventional dipping, microwave dipping and ultrasonic immersing during dipping, is good with conventional infusion process.Co-impregnation is after main active constituent molecular sieve is soaked the solubility solution that contains nonmetal phosphorus (or alkaline-earth metal) and rare earth elemental metals altogether, add inorganic oxide binder and extrusion aid moulding, after the steam treatment, handle with aqueous solutions of organic acids, dipping contains the solubility solution of transition elements metal again; Step impregnation method promptly contains main active constituent molecular sieve dipping the solubility solution of nonmetal phosphorus or alkaline-earth metal earlier, and then the dipping contain the solubility solution of rare earth elemental metals after, add inorganic oxide binder and extrusion aid moulding, after the steam treatment, handle with aqueous solutions of organic acids, last dipping again contains the solubility solution of transition elements metal.
Described inorganic oxide binder is solid or colloidal sol, and wherein solid is one or more the compound in aluminium oxide, silica, imvite, the kaolin, is good with silica; Colloidal sol is one or both the compound in Ludox, the aluminium colloidal sol.
Described extrusion aid can be sesbania powder, polybasic carboxylic acid or the compound of the two, is good with the sesbania powder; Wherein polybasic carboxylic acid can be one or more the sour mixtures in citric acid, oxalic acid and the tartaric acid, calculates with the weight of molecular sieve, and the addition of extrusion aid is 1～15wt%, preferred 2～10wt%.
Described organic acid is one or more the sour mixtures in formic acid, acetate, malonic acid, the butyric acid, is good with acetate.
The Preparation of catalysts method that preparing propylene from C 4 olefins of the present invention and ethene are used is:
Step 1), with molecular sieve and the aqueous solution that contains the aqueous solution of nonmetal phosphorus or alkaline including earth metal at 60～100 ℃ of dipping 2～10h down, be evaporated under 60～100 ℃ dry, 60～180 ℃ of drying 2～12h, 400～700 ℃ of roasting 3～10h, get a modified catalyst after the cooling
Step 2), with the modified catalyst and the aqueous solution that contains rare earth elemental metals, at 60～100 ℃ of dipping 2～10h down, be evaporated under 60～100 ℃ dry, 60～180 ℃ of down dry 2～12h, 400～700 ℃ of roasting 3～10h get twice-modified catalyst after the cooling
Step 3), twice-modified catalyst and a certain amount of extrusion aid are mixed, add inorganic oxide binder furnishing pastel again, spin or extruded moulding behind the mixing.60～180 ℃ of drying 2～12h, 400～700 ℃ of following roasting 3～10h obtain preformed catalyst after the cooling,
Step 4), with preformed catalyst under 600～900 ℃, handle 2～40h with steam (volume ratio by steam and nitrogen is 1: 5～1: 30), calculate with the weight of every gram preformed catalyst, the amount that per hour feeds steam is 1～10mL; Handle preformed catalyst 3～6 grams by every milliliter of organic acid soln, aqueous solutions of organic acids with 0.1～5mol/L is handled preformed catalyst 1～5h under 60～100 ℃ of temperature, cooling back suction filtration, 60～180 ℃ of drying 2～12h then, 400～700 ℃ of roasting 3～10h, obtain the steam treatment catalyst after the cooling
Step 5), the steam treatment catalyst is added in the aqueous solution that contains the transition elements metal, and to transfer pH with the inorganic acid of 1～10wt% be 1.0～5.0, flood 2～10h down at 60～100 ℃, be evaporated to dry under 60～100 ℃, 60～180 ℃ of drying 2～12h, 400～700 ℃ of roasting 3～10h obtain catalysts after the cooling
Step 6), with catalysts at 400～600 ℃, logical nitrogen or helium, activation processing 1～5h obtains activating catalyst after the cooling.Activating catalyst can be directly used in the catalytic reaction of C 4 olefin cracking system propylene and ethene.
Wherein,
In the step 1), contain the preferred (NH of the aqueous solution of nonmetal phosphorus
4)
2HPO
4The aqueous solution, the preferred Ba (NO of the alkaline-earth metal aqueous solution
3)
2The aqueous solution; Weight with molecular sieve is calculated, and the addition of controlling nonmetal phosphorus is 0.01～10wt%, preferred 0.5～5wt%; The addition of alkaline-earth metal is 0.01～5wt%, preferred 0.1～3wt%.
Step 2) in, contains the preferred La (NO of the aqueous solution of rare earth elemental metals
3)
3Or Ce (NO
3)
3The aqueous solution, in the dipping process, the temperature that slowly raises, agitating solution fully carries out with the assurance dipping process fast.Weight with molecular sieve is calculated, and the addition of control rare earth elemental metals is 0.01～10wt%, preferred 0.1～5wt%.
In the step 3), calculate with the weight of molecular sieve, the addition of control inorganic oxide binder is 2～60wt%, preferred 10～50wt%; The addition of extrusion aid is 1～15wt%, preferred 2～10wt%.
In the step 5), contain the preferred (NH of the aqueous solution of transition elements metal
4)
2WO
4, calculating with the weight of molecular sieve, the addition of control transition elements metal is 0.1～15wt%, preferred 1～10wt%.Inorganic acid is one or more mixed acid in nitric acid, sulfuric acid, the hydrochloric acid, is good with nitric acid.
Embodiment 1
With HY molecular sieve and (NH
4)
2HPO
4The aqueous solution is at 80 ℃ of following dipping 2h, be heated under 80 ℃ dried, 120 ℃ of dry 12h, 580 ℃ of roasting 6h.The P-Y catalyst of the phosphorus modification that obtains and Ce (NO
3)
3The aqueous solution at 80 ℃ of dipping 2h, be heated under 80 ℃ dry, 120 ℃ of dry 12h, 580 ℃ of roasting 6h obtain the P-Ce-Y catalyst.In the P-Ce-Y catalyst, add the silica sol binder of 45wt% and the sesbania powder of 10wt%, mix, extruded moulding, roasting 6h among 120 ℃ of dry 12h, 580 ℃, air.With the P-Ce-Y catalyst after the moulding at 800 ℃, handle 12h with steam (volume ratio by steam and nitrogen is 1: 10), weight with every gram P-Ce-Y catalyst is calculated, the amount that per hour feeds steam is 5mL, acetic acid aqueous solution with 1mol/L stirs 2h (containing catalyst solid 3 grams in every milliliter of organic acid soln) at 90 ℃ then, suction filtration, 120 ℃ of dry 12h, 580 ℃ of roasting 6h; The P-Ce-Y catalyst that obtains is joined (NH
4)
2WO
4In the aqueous solution, and to regulate pH with the dilute sulfuric acid of 2wt% be 2.0,80 ℃ of dipping 2h down, be heated under 80 ℃ dried, 120 ℃ of dry 12h, behind 580 ℃ of roasting 6h, after the cooling the P-Ce-W-Y catalyst, and activation 2h obtains activating catalyst in 500 ℃ nitrogen.The addition of each component is in the catalyst: P:1.0wt%, Ce:1.0wt%, W:1.0wt%.
Appreciation condition: catalyst quality 1.0g, the mass space velocity 1.5h of C 4 olefin
-1, reaction temperature is 550 ℃, and the volume ratio of nitrogen and C 4 olefin is 6: 1, and reaction pressure is 0.1MPa.
The result shows that the C 4 olefin conversion ratio of this catalyst is 80.2%, and propene yield is 35.2%, and yield of ethene is 29.1%.
Embodiment 2
With HZSM-5 molecular sieve and Ba (NO
3)
2The aqueous solution is at 80 ℃ of following dipping 2h, be heated under 80 ℃ dried, 120 ℃ of dry 12h, 580 ℃ of roasting 6h, the Ba-ZSM-5 catalyst, with Ba-ZSM-5 and Ce (NO
3)
3The aqueous solution at 80 ℃ of dipping 2h, be heated under 80 ℃ dried, 120 ℃ of dry 12h, 580 ℃ of roasting 6h, the Ba-Ce-ZSM-5 catalyst.In the Ba-Ce-ZSM-5 catalyst, add the silica sol binder of 45wt% and the sesbania powder of 10wt%, mix extruded moulding, 120 ℃ of dry 12h, roasting 6h in 580 ℃ of air.With the Ba-Ce-ZSM-5 catalyst after the moulding at 850 ℃, handle 10h with steam (volume ratio by steam and nitrogen is 1: 8), weight with every gram Ba-Ce-ZSM-5 catalyst is calculated, the amount that per hour feeds steam is 6mL, acetic acid aqueous solution with 1.5mol/L stirs 2h (containing catalyst solid 5 grams in every milliliter of organic acid soln) at 80 ℃ then, cooling back suction filtration, 120 ℃ of dry 12h, 580 ℃ of roasting 6h; The Ba-Ce-ZSM-5 catalyst that obtains is joined (NH
4)
2MoO
4In the aqueous solution, and be that to regulate pH be 3.0,90 ℃ of dipping 3h down for 5% dilute sulfuric acid with mass fraction, be heated to driedly under 90 ℃, 120 ℃ of dry 12h are behind 580 ℃ of roasting 6h, obtain the Ba-Ce-Mo-ZSM-5 catalyst, activation 2h gets activating catalyst in 500 ℃ nitrogen.The addition of each component is in the catalyst: Ba:1.0wt%, Ce:1.0wt%, Mo:2.5wt%.
Appreciation condition: catalyst quality 1.0g, the mass space velocity 1.5h of C 4 olefin
-1, reaction temperature is 550 ℃, reaction pressure: 0.1MPa, and the volume ratio of nitrogen and C 4 olefin is 6: 1.
The result shows that the C 4 olefin conversion ratio of this catalyst is 83.0%, and propene yield is 36.4%, and yield of ethene is 32.0%.
Embodiment 3:
With HZSM-5 molecular sieve and (NH
4)
2HPO
4The aqueous solution is at 80 ℃ of following dipping 2h, be heated under 80 ℃ dried, 120 ℃ of dry 12h, 580 ℃ of roasting 6h, the P-ZSM-5 catalyst, P-ZSM-5 catalyst and La (NO
3)
3The aqueous solution at 80 ℃ of dipping 2h, be heated under 80 ℃ dried, 120 ℃ of dry 12h, 580 ℃ of roasting 6h, the P-La-ZSM-5 catalyst.In the P-La-ZSM-5 catalyst, add the silica sol binder of 45wt% and the sesbania powder of 10wt%, mix, extruded moulding, roasting 6h among 120 ℃ of dry 12h, 580 ℃, air.With the P-La-ZSM-5 catalyst after the moulding at 800 ℃, handle 12h with steam (volume ratio by steam and nitrogen is 1: 8), weight with every gram catalyst is calculated, the amount that per hour feeds steam is 5mL, acetic acid aqueous solution with 1mol/L stirs 2h (containing catalyst solid 5 grams in every milliliter of organic acid soln) at 90 ℃ then, cooling back suction filtration, 120 ℃ of dry 12h, 580 ℃ of roasting 6h; The P-La-ZSM-5 catalyst of moulding is joined (NH
4)
2WO
4In the aqueous solution, and be that to regulate pH be 3.0,80 ℃ of dipping 2h down for 2% rare nitric acid with mass fraction, be heated to driedly under 80 ℃, 120 ℃ of dry 12h are behind 580 ℃ of roasting 6h, obtain the P-La-W-ZSM-5 catalyst, and activation 2h obtains activating catalyst in 500 ℃ nitrogen.The addition of each component is in the catalyst: P:1.8wt%, La:0.5wt%, W:3.2wt%.
Appreciation condition: catalyst quality 1.0g, the mass space velocity 1.5h of C 4 olefin
-1, reaction temperature is 550 ℃, and reaction pressure is 0.1MPa, and the volume ratio of nitrogen and C 4 olefin is 6: 1.
The result shows that the C 4 olefin conversion ratio of this catalyst is 87.4%, and propene yield is 38.5%, and yield of ethene is 42.1%.
Claims (8)
1. the catalyst used of preparing propylene from C 4 olefins and ethene, it is characterized in that this catalyst comprises that with molecular sieve be main active constituent, with the transition elements metal is auxiliary agent, is modifier with alkaline-earth metal or nonmetal phosphorus, rare earth elemental metals, is the binding agent moulding with resistant to elevated temperatures inorganic oxide; Weight with molecular sieve is calculated, the addition of transition elements metal is 0.1～15wt%, the addition of alkaline-earth metal is 0.01～10wt%, the addition of nonmetal phosphorus is 0.01～10wt%, the addition of rare earth elemental metals is 0.01～10wt%, the addition of inorganic oxide binder is 2～60wt%, and all the other are molecular sieve.
2. the catalyst that preparing propylene from C 4 olefins according to claim 1 and ethene are used is characterized in that described molecular sieve is one or more the mixture in A type or X type or Y type or ZSM type series or the MCM type series.
3. the catalyst that preparing propylene from C 4 olefins according to claim 1 and ethene are used is characterized in that described transition elements metal is the combination of one or several metals in molybdenum, tungsten, the rhenium.
4. the catalyst that a kind of preparing propylene from C 4 olefins according to claim 1 and ethene are used is characterized in that described alkaline-earth metal is the combination of one or more metals in calcium, magnesium, strontium, the barium.
5. the catalyst that preparing propylene from C 4 olefins according to claim 1 and ethene are used is characterized in that described rare earth elemental metals is selected from the combination of one or more metals in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, the europium.
6. the catalyst that preparing propylene from C 4 olefins according to claim 1 and ethene are used, it is characterized in that described inorganic oxide binder is solid or colloidal sol, wherein solid is one or more the compound in aluminium oxide, silica, imvite, the kaolin; Colloidal sol is one or both the compound in Ludox, the aluminium colloidal sol.
7. the Preparation of catalysts method that preparing propylene from C 4 olefins according to claim 1 and ethene are used is characterized in that this Preparation of catalysts method is:
Step 1), with molecular sieve and the aqueous solution that contains the aqueous solution of nonmetal phosphorus or alkaline including earth metal at 60～100 ℃ of dipping 2～10h down, 60～100 ℃ of following heating evaporations are to doing 60～180 ℃ of drying 2～12h, 400～700 ℃ of roasting 3～10h, get a modified catalyst after the cooling
Step 2), with the modified catalyst and the aqueous solution that contains rare earth elemental metals, at 60～100 ℃ of dipping 2～10h down, 60～100 ℃ of following heating evaporations are to doing, 60～180 ℃ of down dry 2～12h, 400～700 ℃ of roasting 3～10h get twice-modified catalyst after the cooling
Step 3), twice-modified catalyst and a certain amount of extrusion aid are mixed, add inorganic oxide binder furnishing pastel again, spin or extruded moulding behind the mixing; 60～180 ℃ of drying 2～12h, 400～700 ℃ of following roasting 3～10h obtain preformed catalyst after the cooling,
Step 4), with preformed catalyst under 600～900 ℃, be 1: 5～1: 30 by the volume ratio of steam and nitrogen, with steam treatment preformed catalyst 2～40h, in the weight of every gram preformed catalyst, the amount that per hour feeds steam is 1～10mL; After the cooling, handle preformed catalyst 3～6 grams, under 60～100 ℃ of temperature, handle preformed catalyst 1～5h with the aqueous solutions of organic acids of 0.1～5mol/L by every milliliter of aqueous solutions of organic acids; Cooling back suction filtration, 60～180 ℃ of drying 2～12h then, 400～700 ℃ of roasting 3～10h obtain the steam treatment catalyst after the cooling,
Step 5), the steam treatment catalyst is added in the aqueous solution that contains the transition elements metal, and to transfer pH with the inorganic acid of 1～10wt% be 1.0～5.0, flood 2～10h down at 60～100 ℃, 60～100 ℃ of following evaporates to dryness, 60～180 ℃ of drying 2～12h, 400～700 ℃ of roasting 3～10h obtain catalysts after the cooling
Step 6), with catalysts at 400～600 ℃, logical nitrogen or helium, activation processing 1～5h obtains activating catalyst after the cooling; Activating catalyst can be directly used in the catalytic reaction of C 4 olefin cracking system propylene and ethene.
8. the Preparation of catalysts method that preparing propylene from C 4 olefins according to claim 7 and ethene are used, it is characterized in that in step 3), extrusion aid is sesbania powder, polybasic carboxylic acid or the compound of the two, wherein polybasic carboxylic acid can be one or more the sour mixtures in citric acid, oxalic acid and the tartaric acid, in the weight of molecular sieve, the addition of extrusion aid is 1～15wt%; Organic acid in the step 4) is one or more the sour mixtures in formic acid, acetate, malonic acid, the butyric acid; Inorganic acid in the step 5) is one or more the sour mixtures in nitric acid, sulfuric acid, the hydrochloric acid.
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