CN103360197B - High-selectivity method for producing propylene by using C4-C8 olefins - Google Patents
High-selectivity method for producing propylene by using C4-C8 olefins Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention provides a high-selectivity method for producing propylene by using C4-C8 olefins. The method comprises the following steps of: introducing raw materials rich in the C4-C8 olefins to a fluidized bed reactor of a catalytic conversion device, and carrying out catalytic conversion reaction through countercurrent contact between the raw materials rich in the C4-C8 olefins and a catalytic cracking catalyst in the fluidized bed reactor to obtain a reaction product and a spent catalyst, wherein the spent catalyst is recycled after being subjected to steam stripping and burned, the reaction product is introduced to a fractionating system so as to be subjected to fractional distillation, and the catalytic cracking catalyst comprises a modified mesoporous molecular sieve. The method provided by the invention is higher in propylene yield when used for converting the raw materials rich in the C4-C8 olefins.
Description
Technical field
The present invention relates to a kind of C
4-C
8alkene transforms the method for producing propylene in fluidized-bed.Furtherly, relate to one in a fluidized bed reactor, utilize under existing containing intermediate pore molecular sieve catalyst and be rich in C
4-C
8the method of the material choice preparing propone of alkene.
Background technology
The method of current a kind of preparing propone is with low value-added alkene such as C
4-C
8alkene contacts generation scission reaction and produces with zeolite containing catalyst, wherein said zeolite is mainly MFI structure zeolite such as ZSM-5 zeolite.For C
4-C
8conversion of olefines, use its productivity of propylene of riser reactor to be difficult to improve, even in order to improve depth of conversion, often cause Propylene Selectivity lower, dry gas yied is higher.
In order to improve C
2and C
3the productive rate of alkene, US6222087B1 discloses a kind of fluidized-bed reactor and silicon-aluminum containing of utilizing than being greater than the ZSM-5 type zeolite catalyst of 300 by C
4-C
7alkene or alkane transformations are the method for small-numerator olefin, but this patent does not relate to how improving C further
4-C
8the productivity of propylene of conversion of olefines.
Existing light olefins produces the fluidization of propylene, and in order to improve depth of conversion, need higher temperature of reaction, corresponding finish Contact Temperature is also higher, and cause Propylene Selectivity to reduce, dry gas yied is higher.
Summary of the invention
The technical problem to be solved in the present invention is to provide one and utilizes fluidized-bed reactor conversion to be rich in C
4-C
8olefin feedstock produces the method for propylene, and the method has higher productivity of propylene.
The invention provides a kind of C
4-C
8conversion of olefines produces the method for propylene, and the method comprises and will be rich in C
4-C
8the raw material of alkene is introduced in the fluidized-bed reactor of catalytic convention design, react with the catalytic cracking catalyst counter current contact introduced in described fluidized-bed reactor, obtain reaction product and reclaimable catalyst, reclaimable catalyst uses through stripping, coke burning regeneration Posterior circle, and reaction product introduces fractionating system fractionation; Wherein said catalytic cracking catalyst comprises modified mesoporous molecular sieve.
C provided by the invention
4-C
8conversion of olefines produces the method for propylene, adopts fluidized-bed reactor, makes containing C
4-C
8the raw material of alkene reacts with the catalyzer counter current contact introduced in reactor, can highly selective by C
4-C
8olefin feedstock preparing low-carbon olefins, has higher productivity of propylene; The density of catalyst reactor can be improved, reduce temperature of reaction.Method provided by the invention, can make C
4-C
8there is polyreaction to a certain degree in alkene, reaction oil gas rises along bed, and the thermocatalyst counter current contact higher with the activity introduced in reactor is reacted, and highly selective generates propylene bottom fluidized-bed reactor on band Pd/carbon catalyst.
Accompanying drawing explanation
Accompanying drawing 1 is the schematic flow sheet of method provided by the invention.
1-fluidized-bed reactor; 2-feed distributor, 21-C
4-C
8olefin feedstock service wire, 22-C
4-C
8olefin feedstock preheat coil; 3-stripper, 31-spent agent outlet line, 32-spent agent flowrate control valve; 4-settling vessel, 41-reaction oil gas outlet line; 5-revivifier, 51-warm air service wire, 52-flue gas outlet line; 6, degassing vessel, 61-catalyst stream control valve, 62 degassed gas service wires; 7-catalyst transport, 71-lift gas service wire, 72-heavy feed stock service wire, 73-catalyst distributor.
Embodiment
C provided by the invention
4-C
8conversion of olefines produces the method for propylene, and described is rich in C
4-C
8the raw material of alkene introduces fluidized-bed reactor by the bottom of fluidized-bed reactor, and react with the catalyst exposure in fluidized-bed reactor bed, reaction product leaves fluidized-bed reactor from the top of fluidized-bed reactor; Described catalytic cracking catalyst is introduced fluidized-bed reactor from the top of fluidized-bed reactor, and reacted reclaimable catalyst is drawn from the bottom of fluidized-bed reactor, thus makes described containing C
4-C
8the raw material of alkene and catalytic cracking catalyst in a fluidized bed reactor counter current contact transform.Reaction product is from the Base top contact of fluidized-bed reactor, follow-up fractionation plant fractionation is introduced after being separated a small amount of catalyzer removing and wherein carry further, the apparatus and method of fractionation can adopt existing method, fractionation can be carried out to reaction product as required, low-carbon alkene (ethene, propylene), gasoline, diesel oil, heavy oil and other hydro carbons can be obtained through fractionation.Reclaimable catalyst is drawn from the bottom of fluidized-bed reactor, thus with the gas-oil separation in fluidized-bed reactor, this reclaimable catalyst through stripping, regeneration Posterior circle use.Described catalytic cracking catalyst is introduced the method for fluidized-bed reactor from top, described catalyzer can be incorporated on fluidized-bed reactor bed, make catalyzer fall into the beds of fluidized-bed reactor by the effect of gravity.
C provided by the invention
4-C
8conversion of olefines is produced in the method for propylene, and described fluidized-bed reactor is selected from one or more in particulate fluidization bed bioreactor, bubbling bed reactor, turbulent bed reactor, fast bed reactor, preferred turbulent bed reactor.Described C
4-C
8olefin feedstock directly sprays into bottom fluidized-bed reactor, contacts with the catalyzer in reactor is reverse, can control the density of catalyst in reaction bed better, can reduce finish Contact Temperature simultaneously.Gas superficial flow velocity in fluidized-bed reactor, generally at below 2m/s, is thus compared with riser reactor, can keep higher beds density, generally at 300kg/m in fluidized-bed reactor
3above, under preferable case, in method provided by the invention, fluidized-bed reactor inner catalyst bed density remains on 350-550kg/m
3.
C provided by the invention
4-C
8conversion of olefines is produced in the method for propylene, is rich in C
4-C
8the raw material of alkene is introduced fluidized-bed reactor from the bottom of fluidized-bed reactor and is reacted, the temperature of reaction is 510-620 DEG C, be preferably 520-580 DEG C, pressure is 0.15-0.3MPa (absolute pressure), is preferably 0.18-0.28MPa (absolute pressure), and the catalytic cracking catalyst of introducing fluidized-bed reactor is rich in C with the described of introducing fluidized-bed reactor
4-C
8the weight ratio (the present invention is also referred to as agent-oil ratio) of olefin feedstock is 8-35: 1, described in be rich in C
4-C
8the weight hourly space velocity that olefin feedstock reacts in a fluidized bed reactor is 0.2-30h
-1, be preferably 0.5-28h
-1.Described is rich in C
4-C
8the raw material of alkene generally through preheating laggard enter in fluidized-bed, preferred preheating temperature is 300-600 DEG C and is more preferably 300-500 DEG C.In method provided by the invention, for reducing oil gas dividing potential drop in reactor, can inject bottom described fluidized-bed reactor in the process of carrying out described catalytic cracking reaction and being selected from water vapour, nitrogen, hydrogen, C
1-C
4the thinner of one or more in alkane, carbonic acid gas, carbon monoxide, wherein, preferably water steam, the weight ratio of thinner and hydrocarbon raw material is preferably 0.01-1: 1, and when thinner is water vapour, this ratio also claims water-oil ratio.
C provided by the invention
4-C
8conversion of olefines is produced in the method for propylene, and described is rich in C
4-C
8the raw material of alkene, green coke is lower, can improve preheating temperature to a certain extent, thus better setting device self thermal equilibrium, described in be rich in C
4-C
8the raw material of alkene is preferably preheated to 300-500 DEG C.Be rich in C
4-C
8the raw material raw material of alkene can carry out heat exchange with product stream, or is heated by process furnace, or by carrying out heat exchange with catalyst stream, obtains enough heats.A kind of preferred method, as shown in Figure 1, is rich in C
4-C
8the raw material of alkene, after being preheated to certain temperature such as 250-350 DEG C, spraying into preheat coil 22 by pipeline 21 and is preheated to 300-500 DEG C, then entered bottom fluidized-bed reactor by feed distributor 2 together with thinner preferably water steam.
C provided by the invention
4-C
8conversion of olefines is produced in the method for propylene, C used
4-C
8olefin feedstock is for being rich in C
4-C
8the raw material of alkene, described is rich in C
4-C
8the raw material of alkene comprises C
4, C
5, C
6, C
7, C
8one or more in alkene, C
4-C
8the total content of alkene is greater than 20 % by weight, is preferably 30-100 % by weight, is more preferably 50-100 % by weight.
C provided by the invention
4-C
8conversion of olefines is produced in the method for propylene, comprise modified mesoporous molecular sieve, described modified mesoporous molecular sieve is phosphorus and transition metal modified mesoporous molecular sieve, described transition metal comprise in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi and RE one or more.With the gross weight of described catalytic cracking catalyst for benchmark, the described phosphorus containing 1-60 % by weight in described catalytic cracking catalyst and transition metal modified mesoporous molecular sieve, the heat-resistant inorganic oxide of 5-99 % by weight and the clay of 0-70 % by weight.Silica alumina ratio (the SiO of described phosphorus and transition metal modified mesoporous molecular sieve
2/ Al
2o
3) be preferably 20-290, be more preferably 40-100; In described catalytic cracking catalyst, described phosphorus and transition metal modified mesoporous molecular sieve content are preferably 15-55 % by weight, are more preferably 20-50 % by weight.
Described phosphorus and transition metal modified mesoporous molecular sieve are phosphorus and transition metal modified SAPO molecular sieve and/or phosphorus and the transition metal modified molecular sieve with MFI structure, described transition metal comprise in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi and RE one or more.In described phosphorus and transition metal modified mesoporous molecular sieve, the content of phosphorus is with P
2o
5count 1.3-10 % by weight, levels of transition metals is with M
xo
ycount 0.7-15 % by weight, sodium oxide content is that 0-0.3 % by weight, M represents transition metal, M
xo
yrepresent metal oxide, x represents the atomicity of M, and y represents the number needed for oxidation state meeting M.Described phosphorus and transition metal modified mesoporous molecular sieve are preferably the molecular sieve with MFI structure that is phosphorous and transition metal, have the molecular sieves of MFI structure as one or more in ZSM-5 molecular sieve, ZSP molecular sieve, ZRP molecular sieve; More preferably, described phosphorus and transition metal modified mesoporous molecular sieve are the molecular sieve with MFI structure that the is phosphorous and at least one in chosen from Fe, cobalt and nickel, or for being selected from the molecular sieve with MFI structure of the metal-modified phosphorous and rare earth of one or more in VIII race's metal, IB race, II B race and alkaline-earth metal, wherein, described one or more metals be selected from VIII race's metal, IB race, II B race and alkaline-earth metal are no more than 15 % by weight with the total content of oxide basis, and preferably 0.1 ~ 10 % by weight; Further preferred, the MFI structure molecular sieve that has of described phosphorous and transition metal comprises iron.When the silica alumina ratio with the molecular sieve of MFI structure of phosphorous and transition metal is at 20-290, preferably during 40-100, in catalyzer, the content of modified mesoporous molecular sieve is at 15-55 % by weight, preferably when 20-50 % by weight, catalyst activity better mates with selectivity, and described catalyzer has higher small-numerator olefin, particularly Propylene Selectivity and productivity of propylene.
Containing 5-99 % by weight in described catalytic cracking catalyst, the heat-resistant inorganic oxide of preferred 8-50 % by weight, described heat-resistant inorganic oxide is be customarily used in one or more in the inorganic oxide of catalytic cracking catalyst, such as ZrO
2, SiO
2, Al
2o
3in one or more.
Containing clay in catalytic cracking catalyst of the present invention, described clay can be natural or synthetic, through or without various chemistry and/or physical treatment, the various clays that are typically used as cracking catalyst carrier, such as, in kaolin, halloysite one or more.The content of described clay is no more than 70 % by weight, is preferably 10-60 % by weight.Preferably, described modified mesoporous molecular sieve, the heat-resistant inorganic oxide of 8-50 % by weight and the clay of 10-60 % by weight containing 15-55 % by weight in described catalytic cracking catalyst.
Preferably, also containing large pore molecular sieve in described catalytic cracking catalyst, its content is preferably 1-15 % by weight, described large pore molecular sieve is selected from layered molecular sieve and/or Y zeolite, be more preferably layered molecular sieve, described layered molecular sieve is modification rectorite (its content is with the dry basis of rectorite) such as.Described modification rectorite is introduce inorganic oxide upholder in rectorite expanding layer, carry out modulation to the structure of rectorite to obtain, wherein inorganic oxide preferably accounts for the 10-20 % by weight of rectorite weight, one or more in the optional self-alumina of described inorganic oxide, silicon oxide, zirconium white, preferential oxidation aluminium.Described modification rectorite can be previously prepared, also can be to obtain in the plastic process modification of catalyzer.Time previously prepared, the preparation method of described modification rectorite can be as follows: by rectorite, the precursor being used for the inorganic, metal oxide of modification, the mixing of decationized Y sieve water, be mixed with the slurries that solid content is 25-50 % by weight, stir 3-5 hour at normal temperatures, wherein rectorite: described inorganic oxide precursor (with oxide basis) weight ratio=100: 10-100 preferably 100: 12-30, gained slurries are used further to catalyst preparation process after namely can be used for catalyst preparation process or drying; The precursor of wherein said inorganic, metal oxide is as one or more in Alumina gel, pseudo-boehmite, silicon sol, zirconium colloidal sol.In preparing in the plastic process at catalyzer, can by rectorite, molecular sieve, other clay (such as kaolin), heat-resistant inorganic oxide precursor mixes, or also add heat-resistant inorganic oxide, be mixed with the slurries that solid content is 25-50 % by weight, stir 2-5 hour at normal temperatures, wherein rectorite: inorganic oxide precursor (with oxide basis) weight ratio is not less than 100: 12, be preferably 100: 12-500 preferably 100: 12-400, preferably, described modification makes in the modification rectorite obtained containing the inorganic oxide accounting for rectorite weight 10-20 % by weight.Described normal temperature is generally 15-40 DEG C.Add the catalyzer finally roasting 1-7 hour preferred 3-6 hour at 500-600 DEG C of rectorite.When described large pore molecular sieve is modification rectorite, with the weighing scale of rectorite, described in described catalytic cracking catalyst, the content of modification rectorite is preferably 1-15 % by weight, more preferably 1.5-12 % by weight.
C provided by the invention
4-C
8conversion of olefines is produced in the method for propylene, and the reclaimable catalyst of drawing at the bottom of described fluidized-bed reactor introduces stripper stripping, and then introduce revivifier regeneration, the catalyst recirculation after regeneration uses.The method of regeneration is existing method, and the temperature of regeneration is generally 680-720 DEG C.Be regenerated catalyst through catalyst transport pipeline by the top promoting medium and rise to described fluidized-bed reactor, lifting medium is water vapour, nitrogen, hydrogen, C
1-C
4the mixture of one or more in alkane, carbonic acid gas, carbon monoxide.Preferably, in catalytic cracking catalyst lifting process, introduce heavy feed stock to catalyst transport pipeline to contact with described catalytic cracking catalyst, make described catalytic cracking catalyst hangs charcoal, carbon hanging rate (the charcoal weight on catalyzer accounts for the percentage of catalyst weight) at 0.05-0.9 % by weight, preferred 0.1-0.5 % by weight.Under normal circumstances, during described heavy feed stock contacts with described catalytic cracking catalyst, the weight ratio of described catalytic cracking catalyst and described heavy feed stock is 5-50: 1, and duration of contact is 0.5-5 second, and when described contact makes to enter fluidized-bed reactor, the temperature of catalyzer is 550-650 DEG C.Contacting with described catalytic cracking catalyst by introducing heavy feed stock at line of pipes, both to catalyzer, there is modifying function, and improving Propylene Selectivity and productive rate, can C be solved again
4-C
8olefin catalytic is converted into the shortage of heat problem in propylene process.Described heavy feed stock can be one or more in catalytic diesel oil, catalytic slurry, decompressed wax oil, long residuum, vacuum residuum.Described heavy feed stock can be the self-produced heavy oil of process of the present invention, also can from external device (ED).
Described reaction product introduces fractionating system, is separated, can obtains H
2-C
2, C
3cut, C
4cut, C
5cut, C
6+ gasoline fraction, C
6+ gasoline fraction can be separated into C6 cut and C further
7above cut, wherein C
3in cut, propylene content is more than 88 % by weight, can be separated further and obtain highly purified propylene.Be separated the H obtained
2-C
2partly can return riser tube as lifting medium, modifying function be played to catalyzer simultaneously.Be separated the C obtained
4, C
5, C
6cut partly can return fluidized-bed reactor bed and continue reaction, to obtain maximum productivity of propylene.Be separated the C obtained
7above cut is rich in aromatic hydrocarbons usually.
C provided by the invention
4-C
8conversion of olefines is produced in the method for propylene, will be rich in C
4-C
8the raw material of alkene is in the fluidized-bed reactor of catalytic convention design, contact with catalytic cracking catalyst and carry out catalytic cracking reaction, reaction product is drawn with reclaimable catalyst from described reactor and is separated, isolated reclaimable catalyst is through stripping, used by Returning reactor internal recycle after coke burning regeneration, isolated reaction product introduces fractionating system fractionation can obtain low-carbon alkene, diesel oil, heavy oil and other low molecule saturated hydrocarbons again.Described catalytic convention design comprises at least fluidized-bed reactor, settling vessel, stripper and revivifier, wherein, described stripper is positioned at the below of fluidized-bed reactor, and stripper is communicated with the bottom of fluidized-bed reactor, and the outlet of fluidized-bed reactor is communicated with the entrance of the gas-solid separation equipment in described settling vessel, the catalyst outlet of the gas-solid separation equipment of described settling vessel is communicated with fluidized-bed reactor.Stripper is made to be positioned at the below of fluidized-bed reactor, and stripper is communicated with the bottom of fluidized-bed reactor, thus, the water vapour supplied in stripper upwards can obtain second stage employ by fluidized-bed reactor as the water filling steam of the catalytic cracking reaction wherein occurred, and is conducive to the overall energy consumption reducing reaction.
Below in conjunction with accompanying drawing 1, method provided by the present invention is further detailed, but does not therefore limit the present invention.
Fig. 1 is C provided by the invention
4-C
8olefins process schematic flow sheet.This schematic diagram is simple flow, but does not affect those of ordinary skill in the art's the understanding of the present invention.
Catalytic convention design described in Fig. 1, comprise fluidized-bed reactor 1, settling vessel 4, stripper 3 and revivifier 5, preferred described stripper 3 is positioned at the below of described fluidized-bed reactor 1, and stripper 3 is directly communicated with the bottom of fluidized-bed reactor 1, the top oil gas vent of described fluidized-bed reactor 1 is communicated with the entrance of the gas-solid separation equipment in described settling vessel 4, and the catalyst outlet of settling vessel 4 cyclonic separator is communicated with fluidized-bed reactor bottom.Because stripper 3 is communicated with fluidized-bed reactor 1 gas-solid, therefore, discharged the flowrate control valve 31 of reclaimable catalyst to revivifier 5 by adjustment stripper 3, can the direct charge level of catalyzer in control flow check fluidized bed reactor 1, and then the weight hourly space velocity of reaction in control flow check fluidized bed reactor 1, technique flexibility ratio can be increased thus.Preferably, described settling vessel 4, fluidized-bed reactor 1 and stripper 3 are coaxial, and settling vessel 4 is positioned at above described fluidized-bed reactor 1, and stripper 3 is positioned at below fluidized-bed reactor 1, the catalyst outlet of described settling vessel 4 gas-solid separation equipment is communicated with fluidized-bed reactor bottom.Introduce revivifier 5 coke burning regeneration after the reclaimable catalyst stripping of carbon deposit with activity recovery, and revivifier is communicated with catalytic cracking reaction device, to provide the thermocatalyst after regeneration to reactor by least one catalyst transport path.Make stripper be positioned at the below of fluidized-bed reactor, and stripper is communicated with the bottom of fluidized-bed reactor.Thus, the water vapour supplied in stripper upwards can obtain second stage employ by fluidized-bed reactor as the water filling steam of the catalytic cracking reaction wherein occurred, and is conducive to the overall energy consumption reducing reaction.
Reclaimable catalyst after stripping is delivered to revivifier 5 through pipeline 31 and guiding valve 32 and is regenerated.Warm air enters revivifier 5 by pipeline 51, and the flue gas that catalyzer coke burning regeneration produces leaves revivifier by pipeline 52.Regenerated catalyst is delivered in fluidized-bed reactor 1 by regenerated catalyst lift line 61 and reuses after degassing vessel 6 is degassed.Regenerated catalyst enters catalyst transport 61 after degassing vessel 6 is degassed, wherein control regenerated catalyst flow by control valve 61, introduce by 71 and promote medium, catalyzer enters fluidized-bed reactor by sparger 73, after contacting with hydrocarbon ils in fluidized-bed, draw fluidized-bed reactor from the bottom of fluidized-bed.The pre-lift gas that wherein said lifting medium can select catalytic cracking conventional, such as, in water vapour, dry gas one or more.Sparger 73 can higher than fluidized-bed reactor bed end face, catalyzer is made to drop in beds by action of gravity, in order to improve productivity of propylene, catalyzer in catalyst transfer line 7 rises to certain altitude, introduce a certain amount of heavy feed stock by pipeline 72 to catalyst transfer line 7, to carry out modification to catalyzer, then the catalyzer of this modification is incorporated in fluidized-bed reactor by sparger 65, this is not only conducive to improving productivity of propylene, also helps and solves C
4-C
8hydrocarbon transforms the problem of green coke quantity not sufficient.
Be rich in C
4-C
8the raw material of alkene is by feeding line 21, preheat coil 22 and feed distributor 2 are incorporated in fluidized-bed reactor, contact with the catalytic cracking catalyst in fluidized-bed, generate the oil gas being rich in small-numerator olefin, carry catalyzer in this oil gas to be separated with gas-solid separation equipment wherein through settling vessel 4, be separated the catalyzer obtained and return (not shown) bottom fluidized-bed reactor 1, isolated reaction product leaves reactive system via pipeline 41, enter follow-up fractionating system, be separated as required and obtain corresponding cut, such as can be separated into dry gas (H
2-C
2), C
3cut, C
4cut and C
5above cut, is separated and obtains C
4cut partly can return fluidized-bed reactor by fluidized-bed reactor feeding line 21 and react further, generates propylene.C
5above cut is separated further by separating device, can obtain C
5cut, C
6cut, C
7above cut, is separated and obtains C
5, C
6cut partly can return fluidized-bed reactor by fluidized-bed feeding line 21 and react further, generates propylene.Be rich in the C of propylene
3cut, by isolation technique well known to those skilled in the art, obtains high-purity propylene.The dry gas that separation obtains partly can enter regenerated catalyst lifting transfer limes by pipeline 71 and serve as lifting medium.
The following examples will be further described present method, but therefore not limit present method.
The material used in embodiment and comparative example is as follows:
Hydrochloric acid is produced by Beijing Chemical Plant, chemical pure, concentration 36-38 % by weight;
Kaolin is produced by Kaolin of Suzhou company, and solid content is 74.0 % by weight;
Pseudo-boehmite is Shandong Aluminum Plant's Industrial products, and solid content is 62.0 % by weight;
Alumina gel is Shandong catalyzer branch office of stock company of China Petrochemical Industry product, Al
2o
3content is 21.5 % by weight;
ZSP molecular sieve (solid content is 97.8 % by weight, phosphorus content 4 % by weight, iron level 2 % by weight), to be produced by Shandong catalyzer branch office of stock company of China Petrochemical Industry.
Rectorite (also known as rectorite leng, From Zhongxiang Hubei distinguished personages rectorite leng Science and Technology Co., Ltd. product, composition is in table 2).
Usedly be rich in C
4-C
8the feedstock property of alkene is in table 3.
Catalyst Preparation Example
ZSP molecular sieve, kaolin, rectorite and pseudo-boehmite is got according to proportioning, add decationized Y sieve water and Alumina gel is pulled an oar 120 minutes, in alumina weight, the ratio of pseudo-boehmite and Alumina gel is 1: 1, obtain solid content 30 % by weight slurries, the pH value regulating slurries with hydrochloric acid is 3.0, mixture is continued making beating 45 points of kinds, then the slurries spraying dry will obtained, obtains the microballoon that average particulate diameter is 65 microns.By microballoon roasting 1 hour at 500 DEG C.Obtain catalyst B.
According to the method described above, when not adding rectorite, obtained containing 35 % by weight ZSP molecular sieves, 45 % by weight kaolin, 20 % by weight Al
2o
3microspherical catalyst A.
According to as above method Kaolinite Preparation of Catalyst C, D and contrast medium, the composition of catalyzer is as shown in table 1.
Table 1
Table 2
| F | Na 2O | MgO | Al 2O 3 | SiO 2 | P 2O 5 | SO 3 | K 2O |
| 0.17 | 1.4 | 0.55 | 39.3 | 42.5 | 0.52 | 2.5 | 1.6 |
| CaO | TiO 2 | Cr 2O 3 | Fe 2O 3 | SrO | Y 2O 3 | ZrO 2 | |
| 4.7 | 3.5 | 0.12 | 2.9 | 0.19 | 0.065 | 0.093 |
It is weight percentage in table 2.
Table 3
Table 4
Reacting absolute pressure in embodiment and comparative example is 0.21MPa.
Embodiment 1
By catalyzer at 760 DEG C, with 100% steam aging 10 hours, use medium-sized tester, wherein fluidized-bed reactor internal diameter is 64 millimeters, and be highly 1 meter, fluidized-bed reactor top is communicated with settling vessel, bottom is communicated with stripper, and the loading amount of catalyst reactor is 60 kilograms.Wherein, catalyzer adds above fluidized-bed reactor, drop in fluidized-bed reactor bed by action of gravity, reclaimable catalyst flows out from fluidized-bed bottom and enters stripper, sprays into the raw material being rich in alkene, reaction conditions and the results are shown in Table 5 in fluidized-bed reactor, the raw material preheating temperature being rich in alkene is 300 DEG C, regeneration temperature is 690 DEG C, and lifting medium is water vapour, and temperature is 280 DEG C.The raw material of alkene that is rich in used for the C-4-fraction shown in table 3, catalyzer used catalyst A prepared by Catalyst Preparation Example.
Comparative example 1
Comparative example 1 illustrates that adopting riser tube to add fluidized-bed reactor carries out being rich in C
4-C
8effect during olefin feedstock catalysis conversion method.
By catalyzer at 760 DEG C, with 100% steam aging 10 hours, use medium-sized tester.Wherein the internal diameter of riser reactor is 18 millimeters, is highly 6 meters, and fluidized-bed reactor internal diameter is 64 millimeters, is highly 0.5 meter.In compound reactor, the loading amount of catalyzer is 60 kilograms.Riser reactor bottom sprays into carbon four raw material, reaction conditions and the results are shown in Table 5.
Embodiment 2
According to the method for embodiment 1, unlike the use of catalyzer C.
Comparative example 2
With reference to embodiment 1, unlike the use of catalyzer C, raw material is introduced bottom fluidized-bed reactor, catalyzer is also incorporated into bottom fluidized-bed reactor, the two flows contact in fluidized-bed, reclaimable catalyst and oil gas leave from the top of fluidized-bed reactor, and the reclaimable catalyst after separation introduces stripper, and oil gas introduces fractionation plant fractionation.
Embodiment 3
According to the method for embodiment 1, unlike spraying into heavy oil (character is in table 4) on catalyst transport pipeline, the weight ratio of catalytic cracking catalyst and heavy oil is 40, catalyst transfer line temperature out is 620 DEG C, entering pipeline to the time leaving line of pipes from heavy oil is 1.1 seconds, and on catalyzer, coke content is 0.4 % by weight.
Embodiment 4
According to the method for embodiment 1, be the catalyst B containing rectorite unlike used catalyst.
Embodiment 5
According to the method for embodiment 3, catalyzer is with embodiment 4.
Embodiment 6
According to the method for embodiment 1, it is C5 fraction (forming as shown in table 3) unlike raw material.
Comparative example 3
According to the method for comparative example 2, unlike the use of contrast medium and C5 fraction raw material (forming as shown in table 3), catalyzer and C5 fraction raw material also flow.
Embodiment 7
According to the method for embodiment 1, it is carbon six cut (forming as shown in table 3) unlike raw material.
Embodiment 8
According to the method for embodiment 7, unlike the use of catalyzer D.
Comparative example 4
According to the method for embodiment 7, unlike with contrast medium.
Comparative example 5
With reference to shining comparative example 2, unlike the use of catalyzer D, raw material is carbon six cut (as shown in table 3).
The reaction conditions of embodiment and comparative example and the results are shown in Table 5-7.From table 5-7, the inventive method can improve productivity of propylene, can improve productivity of propylene further, can have lower dry gas yied through the catalyzer hanging charcoal.
Table 5
Table 6
Table 7
| Example | Embodiment 6 | Comparative example 3 | Embodiment 7 | Embodiment 8 | Comparative example 4 | Comparative example 5 |
| Raw material | C5 fraction | C5 fraction | Carbon six cut | Carbon six cut | Carbon six cut | Carbon six cut |
| Catalyzer | A | Contrast medium | A | D | Contrast medium | D |
| Reaction conditions | ||||||
| Temperature of reaction, DEG C | 550 | 550 | 550 | 550 | 550 | 550 |
| Weight hourly space velocity, l/h | 2.4 | 2.4 | 3.2 | 3.2 | 3.2 | 3.2 |
| Water-oil ratio, w/w | 0.46 | 0.46 | 0.25 | 0.25 | 0.25 | 0.25 |
| Agent-oil ratio, w/w | 15 | 15 | 14 | 14 | 14 | 14 |
| Bed density kg/m 3 | 390 | 390 | 390 | 390 | 390 | 390 |
| The catalyzer coke content introduced, % | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
| Catalyzer coke content after stripping, % | 0.45 | 0.45 | 0.48 | 0.48 | 0.48 | 0.48 |
| Material balance, % by weight | ||||||
| H 2-C 2 | 5.45 | 5.51 | 4.26 | 4.29 | 5.47 | 4.35 |
| C 3Cut | 52.66 | 51.32 | 54.02 | 54.32 | 51.67 | 52.82 |
| C 4Cut | 15.29 | 15.83 | 14.59 | 14.28 | 15.82 | 15.13 |
| C 5Cut | 9.8 | 10.2 | 8.5 | 8.45 | 10.08 | 8.8 |
| C 6 +Gasoline | 11.59 | 11.76 | 12.55 | 12.49 | 11.92 | 12.69 |
| Heavy oil | 1.39 | 1.42 | 1.95 | 1.96 | 1.35 | 1.98 |
| Coke | 3.82 | 3.96 | 4.13 | 4.21 | 3.69 | 4.23 |
| Amount to | 100 | 100 | 100 | 100 | 100 | 100 |
| Productivity of propylene, % by weight | 46.87 | 45.45 | 50.24 | 49.97 | 46.56 | 48.89 |
| Propylene/total carbon three | 0.890 | 0.886 | 0.930 | 0.920 | 0.901 | 0.926 |
Claims (8)
1. a C
4-C
8the method of olefin production propylene, comprises and will be rich in C
4-C
8the raw material of alkene is introduced in the fluidized-bed reactor of catalytic convention design, catalytic conversion reaction is carried out with the catalytic cracking catalyst counter current contact introduced in described fluidized-bed reactor, obtain reaction product and reclaimable catalyst, reclaimable catalyst uses through stripping, coke burning regeneration Posterior circle, and reaction product introduces fractionating system fractionation; Wherein said catalytic cracking catalyst comprises the mesoporous molecular sieve of modification; Described modified mesoporous molecular sieve is phosphorus and transition metal modified mesoporous molecular sieve, described transition metal comprise in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi and Re one or more, the silica alumina ratio of described modified mesoporous molecular sieve is 20-290; The temperature of reaction of described fluidized-bed reactor is 510-620 DEG C, and reaction pressure is 0.15-0.3MPa, the catalytic cracking catalyst introducing fluidized-bed reactor and introduces the described of fluidized-bed reactor and be rich in C
4-C
8the weight ratio of olefin feedstock is 8-35, described in be rich in C
4-C
8the weight hourly space velocity that olefin feedstock reacts in fluidized-bed is 0.2-30h
-1.
2. according to C according to claim 1
4-C
8the method of olefin production propylene, it is characterized in that, introduce in fluidized-bed reactor after described catalytic cracking catalyst contacts with heavy oil and react, duration of contact is 0.5-5 second, and described contact makes the coke content entered on the cracking catalyst catalyzer of fluidized-bed reactor be 0.1-0.5 % by weight.
3. according to C according to claim 2
4-C
8the method of olefin production propylene, it is characterized in that, described catalytic cracking catalyst contacts with heavy oil, make the coke content on cracking catalyst catalyzer when entering fluidized-bed reactor be 0.1-0.5 % by weight, make the temperature of described catalytic cracking catalyst during introducing fluidized-bed reactor be 550-650 DEG C.
4. according to C according to claim 1
4-C
8the method of olefin production propylene, is characterized in that, described catalytic cracking catalyst comprises: the described phosphorus of 1-60 % by weight and transition metal modified mesoporous molecular sieve, the heat-resistant inorganic oxide of 5-99 % by weight and the clay of 0-70%; In described phosphorus and transition metal modified mesoporous molecular sieve, the content of phosphorus is with P
2o
5count 1.3-10 % by weight, levels of transition metals is with M
xo
ycount 0.7-15 % by weight, sodium oxide content is no more than 0.3 % by weight, M and represents transition metal, and x represents the atomicity of M, and y represents the number needed for oxidation state meeting M.
5. according to C according to claim 4
4-C
8the method of olefin production propylene, is characterized in that, described catalytic cracking catalyst comprises: the described modified mesoporous molecular sieve of 15-55 % by weight, and the silica alumina ratio of described modified mesoporous molecular sieve is 40-100.
6. according to the C described in claim 1,4 or 5
4-C
8the method of olefin production propylene, it is characterized in that, described phosphorus and transition metal modified mesoporous molecular sieve are the molecular sieve with MFI structure of at least one in phosphorous and chosen from Fe, cobalt and nickel and/or the molecular sieve with MFI structure for being selected from the metal-modified phosphorous and rare earth of one or more in group VIII metal, I B race, II B race and alkaline-earth metal.
7. according to the C described in claim 4 or 5
4-C
8the method of olefin production propylene, is characterized in that, described catalytic cracking catalyst contains modification rectorite and/or the Y zeolite of 1-15 % by weight.
8. according to the C described in any one of Claims 1 to 5
4-C
8the method of olefin production propylene, is characterized in that, described fluidized-bed reactor is selected from one or more in particulate fluidization bed bioreactor, bubbling bed reactor, turbulent bed reactor, fast bed reactor; In described fluidized-bed reactor, the bed density of described catalytic cracking catalyst is 350-550kg/m
3.
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| CN102051213A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Catalytic cracking method |
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| CN1493659A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Catalytic conversion method using C4 fraction to increase small molecule olefine hydrocarbon yield |
| CN1676499A (en) * | 2004-04-02 | 2005-10-05 | 中国石油化工股份有限公司 | Method for preparing low carbon number olefin by catalytic pyrolysis |
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