CN100469743C - Preparing process for propylene with gasoline - Google Patents
Preparing process for propylene with gasoline Download PDFInfo
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- CN100469743C CN100469743C CNB2005101319782A CN200510131978A CN100469743C CN 100469743 C CN100469743 C CN 100469743C CN B2005101319782 A CNB2005101319782 A CN B2005101319782A CN 200510131978 A CN200510131978 A CN 200510131978A CN 100469743 C CN100469743 C CN 100469743C
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Abstract
The propylene preparing process with gasoline includes making gasoline containing olefin with water and catalyst to obtain propylene and gasoline product with lowered olefin content. The catalyst has gradient regular structure and includes regular carrier and active component coating distributed in the inner and/or outer surface, and the active component coating has gradient thickness distribution along the axis of the carrier pore canal and is one kind of composite comprising matrix and molecular sieve. The present invention has olefin converting rate of 60-70 % and 45-55 % of olefin is converted into propylene selectively, and can produce great amount of propylene while lowering the content of olefin in gasoline.
Description
Technical field
The invention relates to a kind of method of gasoline system propylene.
Background technology
Propylene is a kind of important Organic Chemicals, and demand in recent years is increasing, and year growth rate of demand has surpassed ethene.The main method of existing industrial acquisition propylene has two classes at present, and first kind is the steam heat cracking of petroleum naphtha in the blank pipe reactor, and second kind is catalytic pyrolysis and the catalytic pyrolysis of heavy crude in fluidized-bed.
The steam heat cracking technique is to be raw material with the petroleum naphtha, when having water vapor to exist, generates light olefin 750-850 ℃ of following thermo-cracking, mainly produces ethene, propylene, and propylene/ethylene about 0.65, is higher than this ratio than maximum limit, and the total olefin productive rate will descend.The high-quality feed naphtha that this process need consumption is a large amount of is the process of a high energy consumption.The propylene of 66-70% is produced with the steam heat cracking technique at present.Because crude oil in China petroleum naphtha content is low, and reformation, cracking etc. are that the course of processing of raw material is fought for raw material with the petroleum naphtha, have aggravated the shortage of petroleum naphtha.
Catalytic pyrolysis is in 500-650 ℃ fluidized-bed, and macromolecular hydrocarbon catalytic pyrolysis is become micromolecular hydrocarbon, obtains gasoline, diesel oil and alkene etc., as ethene, propylene and butylene.
Catalytic pyrolysis is under 650-750 ℃, in fluidized-bed, heavy petroleum hydrocarbon is contacted with the ZSM-5 molecular sieve catalyst that contains Ag or Cu modification, macromolecular heavy petroleum hydrocarbon is converted into micromolecular hydrocarbon, reaches the purpose of voluminous ethene and propylene when obtaining vapour, diesel oil.The propylene of catalytic pyrolysis and catalytic pyrolysis production accounts for the 30-32% of propone output.
Aforesaid method all is to be that raw material is produced propylene with crude oil.
Owing to contain a large amount of alkene in the catalytically cracked gasoline, and alkene is the unclean component of gasoline in gasoline products.Therefore, people are devoted to reduce olefin content in gasoline at present.The existing technology that is used for reducing the gasoline olefin(e) centent that contains alkene is mainly put forth effort on the new selectivity of exploitation and is reduced the new Technology of the catalyzer of olefin(e) centent in the gasoline that contains alkene or auxiliary agent, use or olefin catalytic is changed into other hydrocarbon compound such as ethers, aromatic hydrocarbons or alkane and wait and reach the purpose that reduces olefin(e) centent in the gasoline that contains alkene.Yet, by using the technology that selectivity reduces the catalyzer of olefin(e) centent in the gasoline that contains alkene or the auxiliary agent gasoline products that the direct production olefin(e) centent is low on former catalytic cracking unit at present at most can only olefin(e) centent reduces 15-18% in the gasoline of alkene with containing, can not satisfy actual needs.
The olefin content in gasoline that new technology such as MGD technology can will contain alkene reduces 9-11%, and voluminous liquefied gas and diesel oil, but the cracking again of gasoline has influenced the processing power of device and increased process energy consumption.MOG technology is that conversion of olefines is become C
5 +Component, the alkene total amount can reduce, but aromaticity content also increases simultaneously.
Utilize etherificate, aromizing or alkylation catalyzed reaction conversion of olefines can be become MTBE, aromatic hydrocarbons or alkylate oil, thereby reduce the olefin content in gasoline contain alkene, but MTBE has been inhibited in the gasoline at California, USA and has added at present; And aromaticity content increases, and for a long time also influences the detergency of gasoline; The alkylation catalytic selectivity is bad, influences the composition and the performance of gasoline.
Except above-mentioned shortcoming, the purpose of aforesaid method all is in order to reduce olefin content in gasoline, not put forth effort on the propylene that research becomes the conversion of olefines in the gasoline heavy demand on the market.If unwelcome conversion of olefines in the gasoline can be become the propylene of heavy demand, obviously be a technology that market outlook are arranged very much.
Ordered structure catalyst is a kind of new catalyst, is 700-900 ℃, volume space velocity 60000-80000 hour in temperature
-1Condition under have good activity and selectivity, bed pressure drop is very little, mass-and heat-transfer is effective.This catalyzer mainly is successfully applied to the purifying vehicle exhaust aspect at present, is called for short cleaning catalyst for tail gases of automobiles or Exhaust Gas Catalytic Converter for Automobiles.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming that method of the prior art can not effectively reduce olefin content in gasoline or the conversion of olefines in the gasoline can not be become propylene, provide a kind of and can effectively reduce olefin content in gasoline and make alkene major part in the gasoline change into the gasoline system cyclopropene method of propylene.
The inventor is surprised to find that, by using the gradient ordered structure catalyst, make the active ingredient in the catalyzer on carrier, carry out Gradient distribution, not only can effectively reduce olefin content in gasoline, simultaneously can also make the alkene major part of removing from gasoline change into the propylene of heavy demand on the market, this obviously has extraordinary market outlook.
The invention provides a kind of method of gasoline system propylene, this method comprises that the gasoline that will contain alkene contacts with catalyzer with water, obtain the gasoline products that propylene and olefin(e) centent reduce, wherein, described catalyzer is the gradient ordered structure catalyst, this catalyzer comprises the carrier with ordered structure and is distributed in the active component coating of carrier internal surface and/or outside surface, the thickness of described active component coating distributes along the axial gradient in the duct of the carrier with ordered structure, described active ingredient is a kind of composition, and said composition contains matrix and molecular sieve.
The used gradient ordered structure catalyst of the present invention has the characteristics of ordered structure catalyst, simultaneously because the thickness of active component coating is gradient-structure, by adjusting the distribution of catalyst activity component different positions on carrier, under the situation that does not change the active ingredient total content, make the catalyst activity component carrier axially on form certain Gradient distribution, thereby make the catalytic activity of catalyzer also be Gradient distribution accordingly, the Gradient distribution of this catalytic performance helps realizing the short contact reaction, avoids the selectivity of secondary reaction and raising catalyzed reaction.Specifically, catalyzer of the present invention is by when reaction begins, raw material (as catalytically cracked gasoline) at first reacts with lower air speed through the higher end of active component content, can reach high reaction activity and high, promote the conversion of raw material, axial direction due content of active substance along reaction zone reduces gradually then, reaction velocity increases gradually, thereby reduces the generation of side reaction, reaches and improves optionally purpose.
Experimental results show that, method provided by the invention can reduce the olefin(e) centent in the catalytically cracked gasoline (FCC gasoline) effectively, make the FCC olefin content in gasoline be reduced to 17.2 weight % by 43.6 weight %, also make the alkene that transformed be converted into propylene and ethene simultaneously, make in reducing FCC gasoline, also to produce a large amount of propylene and ethene in the olefin(e) centent with 44% and 8% highly selective.
Description of drawings
Fig. 1 schemes for the SEM of the thickest end end face of gradient ordered structure catalyst that the present invention adopts;
Fig. 2 schemes for the SEM of the thinnest end end face of gradient ordered structure catalyst that the present invention adopts;
The bigger end of gradient ordered structure catalyst thickness that Fig. 3 adopts for the present invention is along the SEM figure of the axial section in carrier duct.
Embodiment
The invention provides a kind of method of gasoline system propylene, this method comprises that the gasoline that will contain alkene contacts with catalyzer with water, obtain the gasoline products that propylene and olefin(e) centent reduce, wherein, described catalyzer is the gradient ordered structure catalyst, this catalyzer comprises the carrier with ordered structure and is distributed in the active component coating of carrier internal surface and/or outside surface, the thickness of described active component coating distributes along the axial gradient in the duct of the carrier with ordered structure, described active ingredient is a kind of composition, and said composition contains matrix and molecular sieve.
The present invention has no particular limits the Gradient distribution of active component coating thickness, as long as passing through, the thickness of active component coating changes in gradient, under the preferable case, active component coating thickness along the axial graded in carrier duct be the 0.1-20 micron/centimetre, be preferably the 1-20 micron/centimetre.Its middle-end active component coating thickness of thick end is preferably the 60-400 micron, and the thickness of the thinnest end active component coating is preferably the 1-60 micron.More preferably the thickness of the thickest end active component coating is the 70-350 micron, and the thickness of the thinnest end active component coating is the 5-50 micron.And the active component coating thickness of ordered structure catalyst of the prior art is the 50-200 micron of homogeneous.Can in all sorts of ways and measure the thickness of coating, for example can adopt SEM, powerful microscope method to measure, the concrete operations of mensuration have been well known in the art, do not repeat them here.
The carrier of ordered structure of the present invention is meant the support of the catalyst of regular parallel duct of the hollow with macro-scale and structured surface.The example of the carrier of described ordered structure includes but not limited to one or more in cordierite honeycomb carrier, mullite honeycomb substrate, cellular alumina carrier and the metal alloy honeycomb substrate.The sectional area that hole, the cross section density of described carrier is preferably 6-140 hole/square centimeter, hole is preferably the 0.4-10 square millimeter, and more preferably hole, cross section density is that the sectional area in 15-100 hole/square centimeter, hole is preferably the 0.6-6 square millimeter.The present invention has no particular limits the structural shape in described hole, can be irregularly shaped for the square of square, trilateral, hexagon, inner spinosity wall or other.
Described active ingredient can be various energy as the compound of catalyst activity component, composition etc., and those skilled in the art are easy to determine the component and the proportioning of active ingredient according to required purposes.For example, according to an aspect of the present invention, described active ingredient can be a kind of composition, and said composition contains matrix and molecular sieve.There is no particular limitation to the content of matrix and molecular sieve in the present invention, for the content of catalyst field routine gets final product.Total amount with composition is a benchmark, and the content of preferred substrate of the present invention is 0-80 weight %, and the content of molecular sieve is 20-100 weight %, and more preferably the content of matrix is 10-75 weight %, and the content of molecular sieve is 25-90 weight %.
Described matrix can be various refractory oxides, for example can be selected from aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, the alkaline earth metal oxide one or more.
Molecular sieve of the present invention can be one or more of various zeolites that can be used for reducing olefin(e) centent and nonzeolite fractionated molecule sieve, for example can be to be selected from zeolite with MFI structure, faujusite, beta-zeolite, omega zeolite, mordenite, the non-zeolite molecular sieve one or more.The zeolite of the described MFI of having structure can be the ZSM-5 molecular sieve, and described faujusite can be y-type zeolite and/or overstable gamma zeolite.Be preferably the y-type zeolite of ZSM-5 molecular sieve, phosphorous and/or rare earth and/or in the overstable gamma zeolite one or more in the specific embodiment of the invention.
Under the preferable case, composition of the present invention also contains the auxiliary agent of 0-10 weight %.Those skilled in the art can be easy to select proper auxiliary agent according to the required catalytic performance that reaches, for example, described auxiliary agent can be selected from one or more in the compound of phosphorus, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, nickel, lanthanum, cerium, cerium-rich mischmetal metal, lanthanum rich norium.The amount of described auxiliary agent can be the amount of above-mentioned auxiliary agent in the conventional catalyst.Total amount with composition is a benchmark, and the content of auxiliary agent is preferably 1-8 weight %.The amount of described auxiliary agent is in constituent content.Described compound can be the form of oxide compound, muriate, vitriol, phosphoric acid salt, nitrate, is preferably the form of water-soluble salt.
Described auxiliary agent may reside in the matrix, also may reside in the molecular sieve, can also be present in simultaneously in matrix and the molecular sieve.The present invention preferably is present in the molecular sieve.
The Preparation of catalysts method with ordered structure that the present invention adopts comprises that the slurry that will contain active ingredient is distributed to the internal surface and/or the outside surface of carrier, then with high pressure gas along carrier shaft to carrying out folk prescription to the purging active ingredient.
Because the distribution that the catalyzer with ordered structure that the present invention adopts only relates to active ingredient improves, therefore the preparation method to the active ingredient slurry has no particular limits.For example, described active ingredient can be commercially available, and also can in all sorts of ways prepares.Different catalyzer, because the composition difference of active ingredient, the preparation method of active ingredient slurry is also slightly different.For example, active ingredient slurry of the present invention for example can prepare by following method: will contain phosphorus, germanium, tin, antimony, bismuth, plumbous, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, nickel, lanthanum, cerium, the cerium-rich mischmetal metal, in the salt of lanthanum rich norium or the compound of other soluble form one or more and solvent, obtain the compounding agent solution that concentration is 10-20 weight %, regulate pH=7.5-12.5 with alkali after solution is heated to 40-90 ℃, stirred 20-120 minute down at 60-85 ℃ then, through suction filtration, wash to water ratio is the wet cake of 40-80 weight %; With molecular sieve and solvent, stir under 40-90 ℃, make the uniform sizing material that solid content is 15-25 weight %, take out the wherein slurry of 10-90 weight %, with remaining slurry acid for adjusting pH=0.5-6, stir after 20-80 minute and mix with the slurry and the above-mentioned wet cake that take out, 40-90 ℃ is stirred after 20-80 minute down, dry, roasting obtains containing phosphorus, germanium, tin, antimony, bismuth, plumbous, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, nickel, lanthanum, cerium, the cerium-rich mischmetal metal, the molecular sieve active ingredient of one or more elements in the lanthanum rich norium.Described solvent is preferably deionized water, the described alkali that is used for regulating pH=7.5-12.5 can be one or more of magnesiumcarbonate, ammoniacal liquor, urea, sodium bicarbonate or sodium carbonate solution, and the described acid that is used for regulating pH=0.5-6 can be one or more of citric acid, dilute hydrochloric acid, dilute sulphuric acid, tartaric acid, carbonic acid.Described exsiccant temperature can be from room temperature to 300 ℃, is preferably 100-200 ℃, and the exsiccant time can be more than 0.5 hour, is preferably 1-10 hour.The temperature of described roasting can be 400-800 ℃, is preferably 500-700 ℃, and the time of roasting can be more than 0.5 hour, is preferably 1-10 hour.
Can the active ingredient slurry be distributed to preparation ordered structure catalyst of the present invention on the internal surface of the carrier with ordered structure and/or the outside surface by the whole bag of tricks, for example can active ingredient be coated on the carrier with ordered structure and prepare ordered structure catalyst by the cladding process of routine.Described coating preferably includes active ingredient is dissolved in the active ingredient slurry that obtains containing active ingredient and solvent in the solvent, and the active ingredient slurry is adjusted to pH=1-7 with acid or alkali, then above-mentioned slurry is coated in carrier internal surface and/or outside surface, carry out folk prescription to purging with high pressure gas along carrier duct direction afterwards, to obtain the active ingredient layer of Gradient distribution.Wherein, it is the 3.5-20 MPa that described high pressure gas are preferably pressure, flow be the 5-50 liter/minute, purge time is preferably 1-10 minute.Described gas can be various not with the gas of carrier and/or active ingredient reaction, as in the zero group gas in air, nitrogen, oxygen, carbonic acid gas, the periodic table of elements one or more.Because air is cheap and be easy to get, therefore preferred described gas is air.Described solvent is preferably deionized water.The feed molar ratio of described active ingredient and deionized water makes that the concentration of active ingredient in slurry is 15-45 weight %, and described to be used for slurry is adjusted to the acid of pH=1-7 or alkali can be one or more of hydrochloric acid, nitric acid, formic acid, acetate, oxalic acid, vinylformic acid, citric acid, ammoniacal liquor, thanomin, quadrol, urea.Described slurry preferably was controlled between the 1-20 micron with the particle diameter of ball milled with active ingredient before applying.Described slurry makes that at the coated weight of carrier internal surface and/or outside surface the thickness of the thickest end active component coating of catalyzer is the 60-400 micron, and the thickness of the thinnest end active component coating is the 1-60 micron.The temperature of described coating is preferably 10-70 ℃, and more preferably 15-35 ℃, the pressure of coating is preferably-0.04 MPa to 0.4 MPa, and the coating time is preferably 0.1-100 second.The method of described coating can be that water is coated with method, pickling process or spraying process.The concrete operations that apply can be carried out with reference to the method described in the CN 1199733C.Under the main preferable case, after purging catalyzer was placed 5-30 minute, the mode of placement is the direction that the carrier duct direction of catalyzer is parallel to gravity.
Preparation of catalysts method of the present invention can also comprise that the active ingredient layer catalyzer with Gradient distribution that will make carries out drying, roasting.The exsiccant temperature is preferably 90-130 ℃, is preferably 3-10 hour time of drying, and more preferably drying temperature is 110-120 ℃, and be 5-7 hour time of drying.
According to the present invention, before applying, tensio-active agent can also be loaded on above-mentioned active ingredient and/or the carrier.Described tensio-active agent is preferably nonionogenic tenside, described nonionogenic tenside is meant and does not produce the tensio-active agent that has poly-hydroxy or polyoxyethylene groups isoreactivity group in ion and the molecule in water, described tensio-active agent is all more stable to bronsted lowry acids and bases bronsted lowry, mainly contains polyvalent alcohol type and polyoxyethylene-type.Preferred nonionic is selected from one or more in polyoxyethylene glycol, glycerol, carboxymethyl cellulose, polyvinyl alcohol or the polyacrylic acid.
The described method that tensio-active agent is loaded on above-mentioned active ingredient and/or the carrier can be that tensio-active agent is dissolved in the deionized water, obtain surfactant soln, and the pH value of solution value is adjusted to 0.5-6.0 or 7.5-9.5, be that 0.5-6.0 or the mixing of 7.5-9.5 surfactant soln contact with above-mentioned active ingredient and/or carrier with gained pH value then, wherein the concentration of surfactant soln is 1-10 weight %.If with in the described active ingredient of tensio-active agent load, then the surfactant soln with the 0.1-10 weight % of relative reactivity dry component basic weight amount mixes with active ingredient.If with in the described active ingredient of tensio-active agent load, then with carrier impregnation in surfactant soln, the time of dipping is 1-300 second.Can surfactant soln pH value be adjusted to 0.5-6.0 with in formic acid, acetate, hydrochloric acid, citric acid or the nitric acid one or more; Can surfactant soln pH value be adjusted to 7.5-9.5 with in ammoniacal liquor, yellow soda ash or the sodium hydroxide one or more.The concentration of surfactant soln is preferably 1-10 weight %.
In order to realize other various modified version purposes, also can in all sorts of ways catalyzer of the present invention is carried out other processing, for example, before applying, earlier carrier is cleaned.Various processing can be used simultaneously also and can use separately, and those skilled in the art are easy to select according to the purpose of required realization.
Because the method for gasoline system propylene of the present invention is actual is by selecting the be converted into propylene of appropriate catalyst with the olefine selective in the gasoline, when reducing olefin content in gasoline, realize rich purpose of producing propylene, therefore the concrete operations that are used for the method for gasoline system propylene of the present invention are had no particular limits, only need to contain the gasoline of alkene, water, the catalyzer contact gets final product, the way of contact of described gasoline and catalyzer is that gasoline is entered from the bigger end of catalyst activity component coat-thickness, discharge from the end that thickness is less, reduce olefin(e) centent and the purpose that produces propylene in the gasoline thereby reach.The weight hourly space velocity that the pressure that the preferred described gasoline that contains alkene of the present invention is 350-850 ℃ with the temperature that water contacts with catalyzer, contact is the 0.1-0.5 MPa, contain the gasoline of alkene is 10-250 hour
-1, water/oily charge ratio is 0.05-5.50.The temperature that more preferably described gasoline, water and the catalyzer that contains alkene contacts is that 450-650 ℃, the pressure of contact are normal pressure to 0.30 MPa, the weight hourly space velocity that contains the gasoline of alkene is 20-180 hour
-1, water/oily charge ratio is 0.05-3.50.
The following examples will the invention will be further described.
Embodiment 1
The preparation of the gradient ordered structure catalyst that present embodiment is used to illustrate that the present invention adopts.
Pseudo-boehmite, iron(ic) chloride, cerous chlorate, Lanthanum trichloride after deionized water for stirring is even, are regulated pH=10.5 with sodium bicarbonate, and constant temperature stirred 110 minutes for 80 ℃, and filtering and washing to water ratio is that the wet cake of 70 weight % is stand-by.
With HZSM-5 molecular sieve (SiO
2/ Al
2O
3Be 100, sodium oxide content is 0 weight %) mix with deionized water, 80 ℃ were stirred homogenizing 30 minutes down, obtained uniform slurry, with the 70 weight % taking-up of slurry.Remaining slurry is regulated pH=4 with citric acid, mixes with the slurry and the wet cake that take out afterwards, and stirs 70 minutes down at 80 ℃, and 130 ℃ were dried by the fire 4 hours down, and 850 ℃ of roastings 6 hours obtain active ingredient.The add-on of HZSM-5 molecular sieve, pseudo-boehmite, iron(ic) chloride, cerous chlorate, Lanthanum trichloride is to make that the content of molecular sieve is 75 weight % in the active ingredient, the content of alumina host is 20 weight %, and the content of ferric oxide, lanthanum trioxide and cerium oxide auxiliary agent is 5 weight %.
With the above-mentioned molecular sieve that contains, the active ingredient of matrix auxiliary agent is mixed with deionized water, regulate pH=4, make the slurry that solid content is 35 weight %, wet ball grinding to particle diameter is 5 microns then, the polyvinyl alcohol solution (regulating pH=4 with formic acid in advance) that will be equivalent to active ingredient butt weight 1.0 weight % afterwards joins in the above-mentioned slurry, stir the back under 15 ℃ in 60 second time, above-mentioned slurry is coated in (Corning Incorporated on the cordierite honeycomb carrier, 100/0.5, hole, cross section density is 15.5 hole/square centimeters, the sectional area in hole is 4.0 square millimeters), and be 5 MPas with pressure, flow be 30 liters/minute high-pressure air along carrier axially carry out folk prescription to purging 6 minutes, then catalyzer was placed 30 minutes after 120 ℃ of dryings 6 hours and obtained gradient ordered structure catalyst of the present invention in 1 hour 600 ℃ of following roastings.The SEM figure of gained gradient ordered structure catalyst as Figure 1-3.As can be seen from the figure, the present invention has made the gradient ordered structure catalyst.Wherein the thickness of the thickest end active component coating is 210 microns, and the thickness of the thinnest end active component coating is 50 microns.Learn that according to calculating the axial gradient that the active ingredient layer forms is 6.4 microns/centimetre on honeycomb substrate.
Embodiment 2
The preparation of the gradient ordered structure catalyst that present embodiment is used to illustrate that the present invention adopts.
Method according to embodiment 1 prepares ordered structure catalyst, different is, the foamed alumina (200/0.33 that described carrier with ordered structure provides for Mount Taishan, Shanghai refractory factory, hole, cross section density is 31 hole/square centimeters, the sectional area in hole is 2.0 square millimeters), the high-pressure air that purges is that pressure is that 7 MPas, flow are 20 liters/minute air, and the time of purging is 5 minutes.In the gradient ordered structure catalyst that obtains, the axial gradient that the active ingredient layer forms on carrier is 10 microns/centimetre, and the thickest end active component coating thickness is 190 microns, 30 microns of the thinnest end active component coating thickness.
Embodiment 3
The preparation of the gradient ordered structure catalyst that present embodiment is used to illustrate that the present invention adopts.
Method according to embodiment 1 prepares ordered structure catalyst, different is, described filter cake is mixed in deionized water by pseudo-boehmite, cupric chloride, zinc chloride, Manganous chloride tetrahydrate, titanium chloride, vanadium chloride and obtains, the iron-chrome-aluminium-alloy honeycomb substrate (400/0.05 that described carrier with ordered structure provides for Yi Mi Imtech, hole, cross section density is 120 hole/square centimeters, the sectional area in hole is 0.8 square millimeter), described molecular sieve is phosphorated y-type zeolite (SiO
2/ Al
2O
3Be 150, phosphorus pentoxide content is 1.5 weight %), the high-pressure air of purging is that pressure is that 17 MPas, flow are 10 liters/minute air, the time of purging is 2 minutes.In the gradient ordered structure catalyst that obtains, the axial gradient that the active ingredient layer forms on carrier is 8.5 microns/centimetre, and the thickest end active component coating thickness is 150 microns, 20 microns of the thinnest end active component coating thickness.
Embodiment 4
Present embodiment is used to illustrate the method for gasoline system propylene provided by the invention.
The gradient ordered structure catalyst that the foregoing description 1 is made is seated in the tubular reactor, be regular reactor, be to inject above-mentioned reactor after the gasoline that contains alkene of 31.2 weight % is preheating to 250 ℃ then with olefin(e) centent, gasoline is entered from the bigger end of catalyst activity component thickness, discharge from the end that thickness is less, inject the water vapor of 250 ℃ of preheatings simultaneously, the weight hourly space velocity that keeps stock oil to inject is 26.7 hours
-1, water/oily charge ratio is 0.15, is that 500 ℃, pressure are normal pressure in temperature of reaction, the products therefrom sampling is analyzed in continuously feeding 2.0 hours.Reaction result sees Table 1.
Embodiment 5
Present embodiment is used to illustrate the method for gasoline system propylene provided by the invention.
The gradient ordered structure catalyst that the foregoing description 2 is made is seated in the tubular reactor, be regular reactor, be to inject above-mentioned reactor after the gasoline that contains alkene of 37.9 weight % is preheating to 280 ℃ then with olefin(e) centent, gasoline is entered from the bigger end of catalyst activity component thickness, discharge from the end that thickness is less, inject the water vapor of 280 ℃ of preheatings simultaneously, the weight hourly space velocity that keeps stock oil to inject is 66.7 hours
-1, water/oily charge ratio is 1.2, is that 550 ℃, pressure are 0.2 MPa in temperature of reaction, the products therefrom sampling is analyzed in continuously feeding 0.5 hour.Reaction result sees Table 1.
Embodiment 6
Present embodiment is used to illustrate the method for gasoline system propylene provided by the invention.
The gradient ordered structure catalyst that the foregoing description 3 is made is seated in the tubular reactor, be regular reactor, be to inject above-mentioned reactor after the gasoline that contains alkene of 43.6 weight % is preheating to 200 ℃ then with olefin(e) centent, gasoline is entered from the bigger end of catalyst activity component thickness, discharge from the end that thickness is less, inject the water vapor of 280 ℃ of preheatings simultaneously, the weight hourly space velocity that keeps stock oil to inject is 100 hours
-1, water/oily charge ratio is 3.0, is that 620 ℃, pressure are 0.25 MPa in temperature of reaction, the products therefrom sampling is analyzed in continuously feeding 1.0 hours.Reaction result sees Table 1.
Table 1
From the result of last table 1 as can be seen, when being used for reducing the catalytically cracked gasoline olefin(e) centent, catalyzer provided by the invention can reduce olefin content in gasoline greatly, olefin conversion is up to 60%, and most of conversion of olefines propylene, ethene of having become separate easily to obtain, obtained unpredictable consequence.
Claims (15)
1, a kind of method of gasoline system propylene, this method comprises that the gasoline that will contain alkene contacts with catalyzer with water, obtain the gasoline products that propylene and olefin(e) centent reduce, it is characterized in that, described catalyzer is the gradient ordered structure catalyst, this catalyzer comprises the carrier with ordered structure and is distributed in the active component coating of carrier internal surface and/or outside surface, the thickness of described active component coating is along the axial distribution gradient in the duct of the carrier with ordered structure, described active ingredient is a kind of composition, said composition contains matrix, molecular sieve and auxiliary agent, described auxiliary agent is present in molecular sieve and/or the matrix, the way of contact of the described gasoline that contains alkene and water and catalyzer is to contain the gasoline of alkene and water enters from the bigger end of catalyst activity component coat-thickness, discharge from the end that active component coating thickness is less, total amount with composition is a benchmark, and the content of described auxiliary agent is 1-10 weight %.
2, method according to claim 1, wherein, described active component coating thickness along the axial graded in carrier duct be the 0.1-20 micron/centimetre.
3, method according to claim 1, wherein, the thickness of the thickest end active component coating of described catalyzer is the 60-400 micron, the thickness of the thinnest end active component coating is the 1-60 micron.
4, method according to claim 1, wherein, the carrier of described ordered structure is the support of the catalyst with the regular parallel duct of hollow and structured surface.
5, method according to claim 4, wherein, the carrier of described ordered structure is selected from one or more in cordierite honeycomb carrier, mullite honeycomb substrate, cellular alumina carrier, the metal alloy honeycomb substrate.
6, method according to claim 5, wherein, hole, the cross section density of described carrier is that the sectional area in 15-100 hole/square centimeter, hole is the 0.6-6 square millimeter.
7, method according to claim 1 wherein, is a benchmark with the total amount of composition, the content of matrix is 10-80 weight %, the content of molecular sieve is 20-90 weight %, and the content of described auxiliary agent is 1-10 weight %, and each components contents sum is 100 weight %.
8, method according to claim 7, wherein, described matrix is selected from one or more in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, the alkaline earth metal oxide.
9, method according to claim 7, wherein, described molecular screening one or more in zeolite, faujusite, beta-zeolite, omega zeolite, mordenite, non-zeolite molecular sieve with MFI structure.
10, method according to claim 9, wherein, the zeolite of the described MFI of having structure is the ZSM-5 molecular sieve, described faujusite is a y-type zeolite.
11, method according to claim 10, wherein, described y-type zeolite is an overstable gamma zeolite.
12, according to claim 1 or 7 described methods, wherein, described auxiliary agent is selected from one or more in the compound of phosphorus, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, nickel, lanthanum, cerium, cerium-rich mischmetal metal, lanthanum rich norium.
13, method according to claim 1, wherein, the described gasoline that contains alkene and the temperature that water contacts with catalyzer are that 350-850 ℃, the pressure of contact are the 0.1-0.5 MPa, the weight hourly space velocity that contains the gasoline of alkene is 10-250 hour
-1, water/oily charge ratio is 0.05-5.50.
14, method according to claim 13, wherein, the described gasoline that contains alkene and the temperature that water contacts with catalyzer are that 450-650 ℃, the pressure of contact are normal pressure to 0.3 MPa, the weight hourly space velocity that contains the gasoline of alkene is 20-180 hour
-1, water/oily charge ratio is 0.05-3.50.
15, according to claim 1,13 or 14 described methods, wherein, the described gasoline that contains alkene refers to catalytically cracked gasoline.
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