CN101684059A - Method for producing propylene and ethylene through catalytic cracking of olefins - Google Patents
Method for producing propylene and ethylene through catalytic cracking of olefins Download PDFInfo
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- CN101684059A CN101684059A CN200810223637A CN200810223637A CN101684059A CN 101684059 A CN101684059 A CN 101684059A CN 200810223637 A CN200810223637 A CN 200810223637A CN 200810223637 A CN200810223637 A CN 200810223637A CN 101684059 A CN101684059 A CN 101684059A
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Abstract
The invention provides a novel method for producing propylene and ethylene through catalytic cracking of olefins, which comprises the steps of: taking C4-C12 olefins as raw materials; and performing acatalytic cracking reaction of the olefins on the raw materials through a catalyst bed to generate the propylene and the ethylene under the conditions that the reaction temperature is between 450 and650 DEG C, the reaction pressure is between 0 and 0.3MPa, the weight space velocity of the olefins is between 1 and 14 h<-1>, and the weight ratio of water to the olefins is 0.1-10, wherein a catalyst comprises a ZSM-5 molecular sieve, an adhesive and a phosphorus element supported on the catalyst, the silicon-aluminum molar ratio SiO2/Al2O3 of the ZSM-5 molecular sieve is 10-300, and the grain diameter of crystal grains of the ZSM-5 molecular sieve is between 10 and 800nm. The method has longer reaction operation time while maintaining the high yield of the propylene and the ethylene, and can be used for industrialized production.
Description
Technical field
The present invention relates to the method for a kind of olefin catalytic cracking to produce propylene and ethene, particularly a kind of is the method that raw material passes through catalytic cracking for producing propylene using, ethene with carbon four～carbon laurylene hydrocarbon.
Background technology
According to statistics, nineteen ninety-five world Ethylene throughput be 7,932 ten thousand tons/year, estimate to 2010 then to be 11,038 ten thousand tons/year.Increase along with ethylene yield, the output of the by-product carbon four of steam cracking and carbon four above alkene constantly increases, be subjected to the influence of factors such as the variation in Chemicals market and transportation cost, it is a kind of approach that utilizes preferably that these low value-added materials are carried out deep processing on the spot.Simultaneously, be subjected to the influence of polypropylene and alkyl aromatic compound demand growth, the propylene demand growth is vigorous.The analyst points out, if do not manage to increase propone output, will reach 5,000,000 tons/year to the breach of propylene in 2010, and therefore, in one period from now on, propylene is considered to have the product of very big market potentiality.At above-mentioned situation, many in the world petro-chemical corporations drop into technology and the catalyzer that strength develops carbon four and carbon four above low value olefin production propylene one after another.
CN1284109A discloses a kind of technology that is used for carbon four above olefin cracking system propylene, ethene, does not add water in the reactive system, and reaction velocity is 10-30 hour
-1, its used catalyzer is a kind of silica alumina ratio greater than 200 hydrothermal modification ZSM-5 molecular sieve, and etherificate carbon four cracking transformation efficiencys are 54% in the embodiment 3, and propene yield only is 29%, and operation 160 hour datas are only arranged.
EPA0109059 discloses a kind of method with carbon four above olefin cracking system propylene, ethene, is catalyzer with silica alumina ratio less than 360 ZSM-5 or ZSM-11 molecular sieve, does not add water in the reactive system, and reaction must be at 50 hours
-1High weight space velocity under carry out, could obtain higher propene yield, and the embodiment that provides also only is the result of several hrs, can not satisfy the requirement of explained hereafter hundreds of hour.
CN1274342A discloses a kind of method of producing ethene and propylene with carbon four to carbon laurylene hydrocarbon.Not adding water in the reactive system, is 16.3 hours when being reflected at 600 ℃, weight space velocity
-1Condition under when carrying out, the propylene selectivity is 45.7%, propene yield is 34.0%.The catalyzer that uses in this method is the ZSM-5 molecular sieve, by ion-exchange, impregnating means catalyzer is carried out modification with Alkali-Metal Na, K and the metal Cu of IB family, Ag etc., prepares the ZSM-5 molecular sieve catalyst that does not contain proton substantially.
It is carbon four to carbon seven conversion of olefiness the technology of propylene and butylene that US5981819 discloses a kind of.Add water vapor in the reactive system, it is said to add the carbon distribution that water vapour can slow down catalyzer, improved the stability of catalyzer.The catalyzer that uses is the Pentasil type molecular sieve catalyst of silica alumina ratio as 10-200, and its BET specific surface is a 300-600 rice
2/ gram, particle diameter is the 0.1-0.9 micron.Do not handle because the ZSM-5 molecular sieve catalyst that uses in this patent carries out modification, so the yield of purpose product propylene is not high, at 462 ℃, the carrying capacity of catalyzer is under the condition of 2 kilograms of catalyzer of per kilogram raw material, and propene yield only is 28.5%.
Chinese patent CN1490287A discloses a kind of method for preparing ethene and propylene, this method comprises that the hydrocarbon mixture with carbon containing four or C 5 monoolefin is a raw material, in fixed-bed reactor, contact with zeolite containing catalyst, and at 350-500 ℃ temperature, pressure and the 1-10h of 0.6-1.0MPa
-1The condition of weight hourly space velocity under react, generate the reaction mixture that contains ethene and propylene, described catalyzer comprises Al
2O
3Or SiO
2Be 20-45%, supersiliceous zeolite (the preferred 200-300 of its silica alumina ratio) is 40-70%, and modified component is 8-20%; Described modified component is selected from least a in oxide compound, alkaline earth metal oxide and the rare-earth oxide of molybdenum oxide, Tungsten oxide 99.999, phosphorus.
Chinese patent CN 1676499A discloses the method that a kind of catalytic pyrolysis prepares olefine in low carbon number, this method is a raw material with carbon four or carbon five hydrocarbon mixtures that do not contain diolefin, with raw material with after water mixes, in fixed-bed reactor with under zeolite containing catalyst contacts, react, generation contains the reaction mixture of propylene and ethene, after refrigerated separation, obtain ethene and propylene, wherein said zeolite containing catalyst is obtained by following component: with the total restatement of raw material, supersiliceous zeolite (the preferred 180-300 of its silica alumina ratio) 20-65%, silicon oxide 20-65%, inorganic oxide 0-20%.Described inorganic oxide is selected from least a in oxide compound, alkaline earth metal oxide and the rare-earth oxide of zirconium white, phosphorus.
The method of a kind of carbon four and above olefin catalytic cracking to produce propylene thereof is disclosed among the CN1506342A.Do not add water vapour in the reactive system, reaction raw materials carbon four and above alkene thereof are 400-600 ℃ in temperature of reaction, and reaction pressure is 0-0.15MPa, and the liquid phase air speed is 10-50 hour
-1Scission reaction takes place under the condition produce propylene.The catalyzer that is used for this process is the ZSM-5 molecular sieve that 0.3-3%, silica alumina ratio example are preferably 80-300 for the alkaline-earth metal loading.
A kind of method that relates to carbon four and above olefin catalytic cracking to produce propylene thereof is disclosed among the CN1611471A.Do not add water vapor in the reactive system, reaction raw materials carbon four and above alkene thereof are 400-600 ℃ in temperature of reaction, and reaction pressure is 0-0.15MPa, and the liquid phase air speed is 2-30 hour
-1Scission reaction takes place under the condition produce propylene.The catalyzer that is used for this process is that 0.6-2.4%, silica alumina ratio are the ZSM-5 molecular sieve of 20-100 for the phosphorus loading.In the embodiment that this patent provides, the air speed of liquid is 10 hours
-1, and the result who reacts 2 hours only is provided.
A kind of method that is used for olefin catalytic cracking to produce propylene, ethene is disclosed among the CN1704389A.By adopting with carbon four-carbon eight alkene is raw material, with the rare earth metal loading is that the ZSM-5 molecular sieve that 0.1-2%, silica alumina ratio example are preferably 80-400 is a catalyzer, in temperature of reaction is 450-650 ℃, reaction pressure is 0-0.2MPa, water/alkene weight ratio is 0.5-5, and the alkene weight space velocity is 0.5-15 hour
-1Produce propylene and ethene under the condition.
Therefore alkene prepares the process of propylene, ethene through catalytic pyrolysis, can take to add water and not add two kinds of technologies of water, and the main ingredient of catalyzer is to have more highly acid molecular sieve.Because the acidity of molecular sieve, carrying out also existing state of conflict and back ideotype side reactions such as alkene oligomerization chainpropagation, hydrogen transference and aromizing when olefins by catalytic cracking prepares propylene, ethene, on the one hand reduced the yield of ethene, propylene, these side reactions may cause coking in the molecular sieve catalyst duct on the one hand, cover chain carrier, make rapid catalyst deactivation.In the technological process that does not add water,, generally be (generally will be at 10 hours by the charging air speed that increases alkene for obtaining higher ethene, propene yield
-1More than) suppress the generation of other side reactions, but catalyzer is because of the fast inactivation rapidly of carbon distribution speed.In adding the water conservancy project skill, to reduce carbon distribution etc. very favourable for suppressing side reaction as thermal barrier and thinner in the adding of water, but the existence of water can cause the framework dealumination of molecular sieve catalyst, thereby catalyst acid density is descended rapidly, and the life-time service of catalyzer is also had certain influence.As seen, add water and do not add two kinds of technological processs of water and respectively have superiority.From catalyst research, though the main active component of catalyzer is ZSM-5, ZSM-11 or SAPO equimolecular sieve, but in order to reach certain catalytic effect, to select the ZSM-5 molecular sieve (from embodiment, the silica alumina ratio of the ZSM-5 molecular sieve that most of effect preferred catalysts is used is greater than 150) of suitable silica alumina ratio on the one hand; Will add suitable modifying element on the one hand, modifying element can be independent thulium or alkali earth metal, can be the common interpolation of basic metal and IB family metallic element, also can be phosphoric.
But, the olefins by catalytic cracking catalyzer that exists in the prior art can not be when guaranteeing high propylene, ethylene yield long-term operation, therefore, for addressing the above problem, it is extremely necessary that a kind of new olefin catalytic cracking to produce propylene and the method for ethene are provided.
Summary of the invention
The purpose of this invention is to provide a kind of new olefin catalytic cracking to produce propylene and the method for ethene.This method has makes the olefins by catalytic cracking reaction keep the characteristics of high propylene, yield of ethene in the cycle than long running.
For realizing purpose of the present invention, the concrete technical scheme that adopts of the method for olefin catalytic cracking to produce propylene of the present invention and ethene is as follows:
With carbon four-carbon laurylene hydrocarbon is raw material, is 450-650 ℃ in temperature of reaction, and reaction pressure is 0-0.3MPa, and the hydrocarbon raw material weight space velocity is 1-14 hour
-1, water/hydrocarbon raw material weight ratio is under the condition of 0.1-10, and hydrocarbon raw material carries out the olefin cracking reaction by beds and generates propylene and ethene, and described catalyzer comprises following component:
A) the silica alumina ratio SiO of 40-75%
2/ Al
2O
3For 10-300, size of microcrystal is the ZSM-5 molecular sieve of 10-800 nanometer;
B) binding agent of 5-60%, described binding agent are selected from silicon oxide, aluminum oxide or their mixture;
C) phosphoric of 0.01-10%;
Wherein said percentage composition is weight percentage, and with the total restatement of catalyzer.
The silica alumina ratio of the type ZSM 5 molecular sieve that adopts in the catalyzer that preferred method of the present invention is used for more than or equal to 20 to smaller or equal to 200; More preferably the silica alumina ratio of type ZSM 5 molecular sieve is 20-180.
The size of microcrystal of the type ZSM 5 molecular sieve described in the catalyzer that preferred method of the present invention is used is the 10-500 nanometer.
In a preferred embodiment of the invention, the silica alumina ratio of described type ZSM 5 molecular sieve is 20-180; Size of microcrystal is the 10-500 nanometer.
The weight content of preferred described ZSM-5 molecular sieve is 50-70%.
The weight content of phosphoric is 0.1-8% in the preferred described catalyzer; More preferably 0.5-8%.
The weight content of preferred described catalyzer middle-weight rare earths metal is 0.1-8%; More preferably 0.5-8%; Further preferred 3-7%.
Preferred described catalyzer middle-weight rare earths metal is selected from least a in lanthanum, cerium, praseodymium and the neodymium.
The weight content of alkaline-earth metal is 0.1-8% in the preferred described catalyzer; More preferably 0.5-8%; Further preferred 3-7%.
Preferred described catalyzer middle-weight rare earths metal is selected from least a in beryllium, magnesium, calcium, strontium, barium and the radium.
Rare earth metal in the described in the method for the invention catalyzer or alkaline-earth metal can exist with the metallic element form, also can exist with its oxide form.
Binding agent can be some binding agents commonly used in the prior art such as silicon oxide, aluminum oxide, kaolin, clay etc. in the catalyzer of method of the present invention, preferred silicon oxide, aluminum oxide or their mixture.
A specific embodiments of the present invention comprises: described catalyzer is by a) SiO of 40-75%
2/ Al
2O
3For 10-300, size of microcrystal is the ZSM-5 molecular sieve of 10-800 nanometer; B) binding agent of 5-60%, described binding agent are selected from silicon oxide, aluminum oxide or their mixture; C) phosphoric of 0.01-10% is formed.
Olefins by catalytic cracking catalyzer of the present invention not only can be made into various difform fixed bed catalysts, equally also can be configured as microspherical catalyst by spraying and be applicable to fluidized bed process technology.
Catalyzer of the present invention can be prepared according to method molecular sieve modified in the prior art, and preferably according to following method preparation, selecting silicon oxide for use with binding agent is that example is described:
1, moulding: with silica alumina ratio, grain size in institute of the present invention claimed range the HZSM-5 molecular sieve and an amount of sesbania powder, silicon oxide powder mix, use an amount of rare nitric acid furnishing mashed prod again, be extruded into the right cylinder that diameter is 3 millimeter then; Through 100-120 ℃ of dry 2-10 hour, 400-800 ℃ roasting 2-20 hour and the bar of certain-length.Usually, the consumption of sesbania powder is that the 2-5% of the gross weight of molecular sieve, silicon oxide gets final product; The consumption of described rare nitric acid does not have special requirement, and the requirement that is fit to extrusion with the mashed prod of furnishing is advisable.
2, the interpolation of phosphoric: the bar that above-mentioned steps is obtained is with the aqueous solution vacuum impregnation at room temperature of the soluble substance (as phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, Secondary ammonium phosphate etc.) that phosphoric can be provided, after dipping back bar is finished liquid-solid separation, at 90-120 ℃ of dry 1-10 hour, bar at 400-800 ℃ of roasting 2-20 hour and after must flooding phosphoric.
3, the interpolation (optionally) of thulium (perhaps alkali earth metal): the bar that above-mentioned steps is obtained is with rare earth metal salt (perhaps alkaline earth salt) solution impregnation of requirement, then 90-120 ℃ of dry 1-10 hour, at 400-800 ℃ of roasting 2-20 hour and bar behind the impregnating metal element.
4, hydrothermal aging is handled: the bar behind the dipping modifying element under 300-800 ℃ temperature steam treatment 2-20 hour.
5, organic acid is handled: the gained bar with solution-treated certain hours such as organic acid such as formic acid, acetate and oxalic acid, citric acids, carried out liquid-solid separation then after hydrothermal aging was handled under the certain temperature condition.
6, catalyzer roasting: got required catalyzer at 400-800 ℃ of roasting 2-20 hour handle the back bar through organic acid.
In Preparation of catalysts process of the present invention, employed raw material is: the molecular sieve raw material is the molecular sieve with MEI structure, as ZSM-5 or ZSM-11, but unlike the prior art, the silica alumina ratio SiO of employed ZSM-5 molecular sieve in the catalyzer of the present invention
2/ Al
2O
3Be preferably 20-200, and the grain size preferable range of molecular sieve is the 10-500 nanometer.The raw material of described modifying element phosphorus is the soluble substance that phosphoric can be provided, such as phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, Secondary ammonium phosphate etc.The raw material of described modified metal is the soluble salt of thulium (perhaps alkali earth metal), as nitrate, and muriate etc.Described binding agent raw material is preferably silicon oxide powder.
Method provided by the invention has following beneficial effect:
1, because the catalyzer that present method is used, the silica alumina ratio of the molecular sieve that adopts is lower, acid density height, be very beneficial for state of conflict and the generations of ideotype side reaction afterwards such as alkene oligomerization chainpropagation, hydrogen transference and aromizing, therefore must take the phosphoric modification, or phosphoric and rare earth metal (perhaps alkaline-earth metal) the element method of modification together, could obtain higher ethene, propene yield.
2, the catalyzer that uses owing to present method, the crystal grain of the molecular sieve of employing is smaller, and when obtaining higher ethene, propene yield, work-ing life is also longer, can satisfy need of industrial production.
Embodiment
Below in conjunction with embodiment the present invention is further elaborated, but the present invention is not produced any restriction.
The preparation method of H type ZSM-5 molecular sieve:
After template is removed in 550 ℃ of following roastings, is 1: 10 ratio in molecular sieve (g) and exchange liquid (ml) with the ZSM-5 molecular screen primary powder of required silica alumina ratio and particle diameter, uses NH
4NO
3Solution (0.8mol/L) exchanges 5h in 90 ℃ of water-baths, filter; Filter cake is used with the exchange liquid of equivalent last time and is exchanged twice repeatedly again, filters, and is washed with distilled water to and does not have NO in the filtrate
3 -Exist, 110 ℃ of dryings, 550 ℃ of roastings promptly obtain the HZSM-5 molecular sieve.
The silicon oxide that uses in following examples and the Comparative Examples is specific surface area＞200M
2The high-purity silicon oxide of/g.
Comparative Examples 1
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 250, and particle diameter is 900nm) is obtained the HZSM-5 molecular sieve according to above-mentioned preparation method's processing.This HZSM-5 molecular sieve and silicon oxide, sesbania powder are mixed in proportion, add an amount of rare nitric acid behind the mixing, be squeezed into diameter 3mm cylinder shape after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silicon oxide.Get a certain amount of cylinder shape particle, use this particle of solution impregnation that contains phosphoric acid under the room temperature, after the filtering separation, 110 ℃ of dryings and in 500 ℃ of roastings, the cylinder shape particle was through 450 ℃ of steam treatment 4 hours after the roasting, handling 5h in 80 ℃ of water-baths of 0.3mol/L acetic acid solution, after the solid-liquid separation 600 ℃ of roastings 4 hours and required catalyst A.
Comparative Examples 2
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 350, and particle diameter is 900nm) is obtained the HZSM-5 molecular sieve according to the processing of above-mentioned preparation side.This HZSM-5 molecular sieve and silicon oxide, sesbania powder are mixed in proportion, add an amount of rare nitric acid behind the mixing, be squeezed into diameter 3mm cylinder shape after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silicon oxide.Get a certain amount of cylinder shape particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the filtering separation, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing Ce (NO
3)
3This particle of solution impregnation, after the filtering separation, 110 ℃ of dryings and in 520 ℃ of roastings, the cylinder shape particle was through 500 ℃ of steam treatment 5 hours after the roasting, handling 3h in 90 ℃ of water-baths of 0.2mol/L citric acid solution, after the solid-liquid separation 600 ℃ of roastings 4 hours and required catalyst B.
Comparative Examples 3
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 150, and particle diameter is 900nm) is obtained the HZSM-5 molecular sieve according to the processing of above-mentioned preparation side.This HZSM-5 molecular sieve and silicon oxide, sesbania powder are mixed in proportion, add an amount of rare nitric acid behind the mixing, be squeezed into diameter 3mm cylinder shape after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silicon oxide.Get a certain amount of cylinder shape particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the filtering separation, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing Ba (NO
3)
2This particle of solution impregnation, after the filtering separation, handle according to Comparative Examples 1 identical condition, required catalyzer C.
Comparative Examples 4
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 50, and particle diameter is 300nm) is obtained the HZSM-5 molecular sieve according to the processing of above-mentioned preparation side.This HZSM-5 molecular sieve and silicon oxide, sesbania powder are mixed in proportion, add an amount of rare nitric acid behind the mixing, be squeezed into diameter 3mm cylinder shape after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silicon oxide.Then with 450 ℃ of steam treatment 6 hours, handling 2h in 90 ℃ of water-baths of 0.2mol/L formic acid solution, after the solid-liquid separation 610 ℃ of roastings 4 hours and required catalyzer D.
Embodiment 1
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 180, and particle diameter is 400nm) is obtained the HZSM-5 molecular sieve according to the processing of above-mentioned preparation side.This HZSM-5 molecular sieve and silicon oxide, sesbania powder are mixed in proportion, add an amount of rare nitric acid behind the mixing, be squeezed into diameter 3mm cylinder shape after stirring evenly, 120 ℃ of dryings and in 550 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silicon oxide.Get a certain amount of cylinder shape particle, use this particle of solution impregnation that contains phosphoric acid under the room temperature, after the filtering separation, 120 ℃ of dryings and in 550 ℃ of roastings, the cylinder shape particle was through 500 ℃ of steam treatment 5 hours after the roasting, handling 3h in 90 ℃ of water-baths of 0.2mol/L citric acid solution, after the solid-liquid separation 600 ℃ of roastings 4 hours and required catalyzer E.
Embodiment 2
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 100, and particle diameter is 200nm) is obtained the HZSM-5 molecular sieve according to the processing of above-mentioned preparation side.This HZSM-5 molecular sieve and silicon oxide, sesbania powder are mixed in proportion, add an amount of rare nitric acid behind the mixing, be squeezed into diameter 3mm cylinder shape after stirring evenly, 120 ℃ of dryings and in 550 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silicon oxide.Get a certain amount of cylinder shape particle, use this particle of solution impregnation that contains phosphoric acid under the room temperature, after the filtering separation, 120 ℃ of dryings and in 550 ℃ of roastings, the cylinder shape particle was through 530 ℃ of steam treatment 4 hours after the roasting, handling 5h in 80 ℃ of water-baths of 0.3mol/L citric acid solution, after the solid-liquid separation 600 ℃ of roastings 4 hours and required catalyzer F.
Embodiment 3
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 120, and particle diameter is 300nm) is obtained the HZSM-5 molecular sieve according to the processing of above-mentioned preparation side.This HZSM-5 molecular sieve and silicon oxide, sesbania powder are mixed in proportion, add an amount of rare nitric acid behind the mixing, be squeezed into diameter 3mm cylinder shape after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silicon oxide.Get a certain amount of cylinder shape particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the filtering separation, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing Ce (NO
3)
3This particle of solution impregnation, after the filtering separation, 110 ℃ of dryings and in 520 ℃ of roastings, the cylinder shape particle was through 500 ℃ of steam treatment 5 hours after the roasting, handling 3h in 90 ℃ of water-baths of 0.2mol/L citric acid solution, after the solid-liquid separation 600 ℃ of roastings 4 hours and required catalyzer G.
Embodiment 4
(silica alumina ratio is 80 with the ZSM-5 molecular sieve, particle diameter is 200nm) former powder handles according to above-mentioned preparation side: the maturing temperature of molecular screen primary powder is become 450 ℃ for 550 ℃, change 3h by 5h swap time, filter cake maturing temperature after the exchange changes 650 ℃ into, other condition is constant, obtains the HZSM-5 molecular sieve.This HZSM-5 molecular sieve and silicon oxide, sesbania powder are mixed in proportion, add an amount of rare nitric acid behind the mixing, be squeezed into diameter 3mm cylinder shape after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silicon oxide.Get a certain amount of cylinder shape particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the filtering separation, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing La (NO
3)
3This particle of solution impregnation, after the filtering separation, 110 ℃ of dryings and in 520 ℃ of roastings, the cylinder shape particle was through 400 ℃ of steam treatment 5 hours after the roasting, handling 8h in 90 ℃ of water-baths of 0.2mol/L acetic acid solution, after the solid-liquid separation 600 ℃ of roastings 4 hours and required catalyzer H.
Embodiment 5
(silica alumina ratio is 50 with the ZSM-5 molecular sieve, particle diameter is 300nm) former powder handles according to above-mentioned preparation side: the maturing temperature of molecular screen primary powder is become 500 ℃ for 550 ℃, change 8h by 5h swap time, filter cake maturing temperature after the exchange changes 600 ℃ into, other condition is constant, obtains the HZSM-5 molecular sieve.This HZSM-5 molecular sieve and silicon oxide, sesbania powder are mixed in proportion, add an amount of rare nitric acid behind the mixing, be squeezed into diameter 3mm cylinder shape after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silicon oxide.Get a certain amount of cylinder shape particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the filtering separation, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing Mg (NO
3)
2This particle of solution impregnation, after the filtering separation, 120 ℃ of dryings and in 620 ℃ of roastings, the cylinder shape particle was through 450 ℃ of steam treatment 6 hours after the roasting, handling 2h in 90 ℃ of water-baths of 0.2mol/L formic acid solution, after the solid-liquid separation 610 ℃ of roastings 4 hours and required catalyst I.
Embodiment 6
(silica alumina ratio is 25 with the ZSM-5 molecular sieve, particle diameter is 100nm) former powder handles according to above-mentioned preparation side: the maturing temperature of molecular screen primary powder is become 540 ℃ for 550 ℃, filter cake maturing temperature after the exchange changes 580 ℃ into, and other condition is constant, obtains the HZSM-5 molecular sieve.This HZSM-5 molecular sieve and silicon oxide, sesbania powder are mixed in proportion, add an amount of rare nitric acid behind the mixing, be squeezed into diameter 3mm cylinder shape after stirring evenly, 120 ℃ of dryings and in 550 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silicon oxide.Get a certain amount of cylinder shape particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the filtering separation, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing Ca (NO
3)
2This particle of solution impregnation, after the filtering separation, 120 ℃ of dryings and in 610 ℃ of roastings, the cylinder shape particle was through 570 ℃ of steam treatment 4 hours after the roasting, handling 6h in 70 ℃ of water-baths of 0.2mol/L citric acid solution, after the solid-liquid separation 590 ℃ of roastings 4 hours and required catalyzer J.
By listing in table 1 respectively the forming of catalyzer that Comparative Examples 1-4 and embodiment 1-6 obtain.
Embodiment 7
Being reflected in the small stationary bed bioreactor of C _ 4 alkene catalytic pyrolysis system propylene, ethene carried out.Reaction tubes is that internal diameter is that 16mm, wall thickness are the stainless steel tube of 2mm, interior dress 25ml catalyzer.Before reaction was carried out, catalyzer activated 2 hours in 500 ℃ under nitrogen atmosphere.After activation finished, C 4 olefin raw material and water were 3h according to the alkene air speed
-1, water/alkene weight ratio is that 0.5 condition is squeezed into preheater and reactor by micro-plunger metering pump, the maintenance reaction pressure is 0.1MPa, temperature of reaction is 520 ℃ and carries out C _ 4 alkene catalytic pyrolysis system propylene, ethylene reaction.Reaction product is got gas phase respectively after refrigerated separation, liquid product is analyzed and carry out material balance calculating.The C 4 olefin transformation efficiency is for transforming the mark that the C 4 olefin quality accounts for alkene quality in the starting raw material, productivity of propylene is the mark that the propylene quality accounts for C 4 olefin quality in the raw material in the product, and ethylene yield is the mark that the ethene quality accounts for C 4 olefin quality in the raw material in the product.
C 4 olefin transformation efficiency and ethene, the productivity of propylene of different catalysts under the differential responses time listed in table 2.From the result of table 2 as can be seen, use method provided by the invention to prepare propylene, ethene, when obtaining than higher propylene, productive rate, the cycle of operation of catalyzer also obviously is longer than prior art.
Table one different catalysts compositing characteristic
Table two different catalysts exists C _ 4 alkene catalytic pyrolysis system ethene, propylene result down
Claims (8)
1, the method for a kind of olefin catalytic cracking to produce propylene and ethene, it is characterized in that: with carbon four-carbon laurylene hydrocarbon is raw material, in temperature of reaction is 450-650 ℃, reaction pressure is 0-0.3MPa, the hydrocarbon raw material weight space velocity is 1-14 hour-1, water/hydrocarbon raw material weight ratio is under the condition of 0.1-10, and hydrocarbon raw material carries out the olefin cracking reaction by beds and generates propylene and ethene, and described catalyzer comprises following component:
A) the silica alumina ratio SiO of 40-75%
2/ Al
2O
3For 10-300, size of microcrystal is the ZSM-5 molecular sieve of 10-800 nanometer;
B) binding agent of 5-60%, described binding agent are selected from silicon oxide, aluminum oxide or their mixture;
C) phosphoric of 0.01-10%;
Wherein said percentage composition is weight percentage, and with the total restatement of catalyzer.
2, method according to claim 1 is characterized in that: the silica alumina ratio of described type ZSM 5 molecular sieve for more than or equal to 20 to smaller or equal to 200.
3, method according to claim 2 is characterized in that: the silica alumina ratio of described type ZSM 5 molecular sieve is 20-180.
4, method according to claim 1 is characterized in that: the size of microcrystal of described type ZSM 5 molecular sieve is the 10-500 nanometer.
5, method according to claim 1 is characterized in that: the weight content of described phosphoric is 0.5-8%.
6, method according to claim 1 is characterized in that: described catalyzer contains thulium or the alkaline-earth metal of 0.5-8%.
7, method according to claim 6 is characterized in that: described rare earth metal is selected from least a in lanthanum, cerium, praseodymium and the neodymium; Described alkaline-earth metal is selected from least a in beryllium, magnesium, calcium, strontium, barium and the radium.
8, method according to claim 1 is characterized in that: described temperature of reaction is 475-625 ℃, and described hydrocarbon raw material weight space velocity is 1-10 hour
-1, described water/hydrocarbon raw material weight ratio is 0.1-3.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276405A (en) * | 2010-06-12 | 2011-12-14 | 中国石油化工股份有限公司 | Method for preparing propylene as main product from C4 and high carbon olefins |
| CN103121891A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin |
| CN103121894A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Combined method for producing low-carbon olefin |
| CN109422607A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | The method for producing ethylene |
| CN109422610A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | The method of increasing output of ethylene |
| CN109422609A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | The production method of ethylene |
| CN109422618A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | The method for producing ethylene and propylene |
| CN112322333A (en) * | 2020-10-21 | 2021-02-05 | 中国石油大学(北京) | Alkane-alkene co-cracking catalyst and alkane-alkene mixed catalytic cracking method |
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2008
- 2008-09-28 CN CN200810223637A patent/CN101684059A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276405A (en) * | 2010-06-12 | 2011-12-14 | 中国石油化工股份有限公司 | Method for preparing propylene as main product from C4 and high carbon olefins |
| CN103121891A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin |
| CN103121894A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Combined method for producing low-carbon olefin |
| CN103121891B (en) * | 2011-11-18 | 2015-07-08 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin |
| CN109422607A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | The method for producing ethylene |
| CN109422610A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | The method of increasing output of ethylene |
| CN109422609A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | The production method of ethylene |
| CN109422618A (en) * | 2017-09-04 | 2019-03-05 | 中国石油化工股份有限公司 | The method for producing ethylene and propylene |
| CN109422610B (en) * | 2017-09-04 | 2022-08-12 | 中国石油化工股份有限公司 | Method for increasing yield of ethylene |
| CN109422609B (en) * | 2017-09-04 | 2022-10-11 | 中国石油化工股份有限公司 | Process for the production of ethylene |
| CN112322333A (en) * | 2020-10-21 | 2021-02-05 | 中国石油大学(北京) | Alkane-alkene co-cracking catalyst and alkane-alkene mixed catalytic cracking method |
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