CN103030503B - Method for preparing propylene by using methanol - Google Patents
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- CN103030503B CN103030503B CN201110300411.9A CN201110300411A CN103030503B CN 103030503 B CN103030503 B CN 103030503B CN 201110300411 A CN201110300411 A CN 201110300411A CN 103030503 B CN103030503 B CN 103030503B
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Abstract
The invention relates to a method for preparing propylene by using methanol, mainly aiming at solving the problems that the regeneration cycle of catalyst for preparing the propylene by using the methanol is short, the hydrogenation reaction temperature is uneasy to control and the equipment investment is great in the prior art. The technical scheme is that the method comprises the following steps that: a) raw materials I containing the methanol enter a reactor to be in contact and react with the catalyst for preparing the propylene by using the methanol to produce a material flow II containing the propylene; b) the material flow II is chilled through a chilling system to obtain a gas material flow III, liquid heavy hydrocarbon and process water, the liquid heavy hydrocarbon is discharged outside and at least part of the process water is returned to the reactor; c) the material flow III enters the upper part of the hydrogenation reaction area of a depropanizing tower, a C3 and below-C3 material flow IV is obtained at the top of the tower, a C4 and above-C4 material flow V is obtained at the bottom of the tower, and at least part of the material flow V is returned to the reactor; and d) the material flow IV enters a C2/C3 separation tower, a C2 and below-C2 material flow VI is obtained at the top of the tower, at least part of the material flow VI is returned to the reactor and C3 fractions are obtained at the bottom of the tower. By adopting the technical scheme, the problems are better solved and the method can be used for the industrial production of the propylene by using the methanol.
Description
Technical field
The present invention relates to a kind of method of preparing propylene from methanol, particularly relate to a kind of catalytic distillation hydrogenation processing method by preparing propylene from methanol.
Background technology
Propylene is one of basic material of modern organic chemical industry.By the growth of the acryloyl derivative demands such as polypropylene, vinyl cyanide, isopropyl benzene, propylene oxide, the demand of corresponding propylene also increases fast.At present, ethene and propylene are mainly by being that the operational path of raw material obtains with oil, and propylene is then mainly derived from the by-product of oil vapour cracking technology and catalytic cracking process.Due to propylene mainly as by-product obtain, so propylene product output is often limited to the output of the major product of its technique.Because propylene demand was always higher than ethene in recent years, in order to produce or propylene enhancing, researchist develops the kinds of processes route such as preparing propylene from methanol (being called for short MTP), conversion of olefines propylene, olefin cracking preparation of propylene.Wherein, MTP production process route utilizes the methyl alcohol etc. that coal or Sweet natural gas are raw material production to transform acquisition propylene product further.
CN1203033C describes the method with preparing propylene from methanol.First methanol steam catalyzed reaction is obtained the mixing steam containing dme by the method, the part C that this steam obtains with reaction
2the part C that following logistics and reaction obtain
4~ C
5logistics mixes, and then by the setting reactor of the filling shape-selective zeolite catalysts of at least 2 series connection, is converted into the mix products based on propylene.The cycle of operation of expection is 500 ~ 700 hours, and then carry out in-situ regeneration, reactor reproduction ratio is more frequent.
In order to improve the selectivity of MTP production technique object product propylene, by-product hydrocarbon is generally taked to carry out circulation technology.Find through experimental study, catalyst for producing propylene with methanol coking speed is comparatively large by the impact of diolefine/alkynes content in circulation by-product hydrocarbon, and wherein C
4the content of above diolefine/alkynes is major influence factors.The alkynes existed in by-product hydrocarbon and diolefine cause the circulation of by-product hydrocarbon to cause, and catalyst deactivation speed is accelerated, cycle of operation shortening.The alkynes of this part generation coke and diolefine are also the losses of product hydrocarbon for MTP technique.In order to reduce catalyzer coking speed, the easy diolefine of coking and the content of alkynes in recycle stock should be reduced as far as possible.By reducing MTP catalyzer green coke speed, the average coke content of MTP catalyzer in the red-tape operati cycle can improve the average propylene selectivity of the MTP technique adopting hydrocarbon circulation further.
Before by-product hydrocarbon circulation Returning reactor, be that monoolefine can solve the problem effectively by hydrogenation technique by the alkynes in logistics and di-olefins.Traditional hydrogenation technique uses hydrogenator to carry out selective hydrogenation, and its shortcoming is that temperature of reactor is wayward, and facility investment is comparatively large, and the remaining hydrogen of hydrogenation forms non-condensable gas in follow-up flow process needs continued emissions.In recent years occurring that catalytic distillation technology carries out selective hydrogenation is good solution route, but is not yet applied in preparing propylene from methanol field at present.Catalytic distillation technology (Catalytic-Distillation Technology) is a kind of in a distillation tower, carry out the novel technique of catalyzed reaction and fractionation by distillation, at first for the production of methyl tertiary butyl ether (MTBE) technique simultaneously.
CN100516176C describes the recovery of ethene and propylene in olefin hydrocarbon apparatus with the hydrogenation of heavy unsaturated compound and be separated.Except to acetylene, C
3alkynes and diolefine carry out outside selective hydrogenation, for C
4and heavier component carries out complete hydrogenation, alkene wherein and alkynes is made all to transform into alkane.For process for preparing propylene from methanol, hydrogenation makes the butylene that wherein can be further converted to propylene product have lost completely, is unfavorable for the yield improving object product propylene.
Summary of the invention
Technical problem to be solved by this invention is when adopting the circulation of by-product hydrocarbon to improve Propylene Selectivity in prior art, methanol-to-propylene catalyst regeneration cycle is short, temperature not easily stability contorting, the larger problem of investment is existed again to by-product hydrocarbon circulation hydrogenation, a kind of method of new preparing propylene from methanol is provided.The method has the advantage that catalyst on-stream cycle time is long, by-product hydrocarbon circulation hydrogenation temperature easily controls, facility investment is little.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing propylene from methanol, comprise: raw material I a) comprising methyl alcohol enters in preparing propylene from methanol reactor and contacts with catalyst for producing propylene with methanol, reaction generates the stream I I comprising propylene; B) stream I I obtains gaseous stream III after chilling, liquid heavy hydrocarbon and process water through quenching system, and liquid heavy hydrocarbon is discharged out-of-bounds, and at least 10 % by weight of process water is back to reactor; C) stream I II enters the top of depropanizing tower hydroconversion reaction zone, obtains C at tower top
3and following stream I V, obtain C at the bottom of tower
4and at least 30 of above logistics V, logistics V % by weight are back to reactor; D) stream I V enters C
2/ C
3knockout tower, obtains C at tower top
2and at least 30 of following logistics VI, logistics VI % by weight are back to reactor, obtain C at the bottom of tower
3cut.
In technical solution of the present invention, the circulating reaction by-product lighter hydrocarbons after selective hydrogenation process and C
4~ C
5enter fixed-bed reactor after hydrocarbon and preparing propylene from methanol reaction raw materials and mixing diluents, under catalyst for producing propylene with methanol effect, be converted into the main reaction product containing propylene.Except containing except alkene in preparing propylene from methanol reaction product, also containing a large amount of byproduct water, C2 alkene, C
4 +alkene, stable hydrocarbon, hydrogen, alkynes, diolefine and a small amount of oxygenatedchemicals etc.Before carrying out separation of olefins, need these by-products to carry out being separated and removing, avoid affecting separation of olefins and propylene product quality.Reaction product enters depropanizing tower (catalytic distillation tower) through initial gross separation process, compression and dried logistics, supplement appropriate hydrogen and carry out selective hydrogenation process under hydrogenation catalyst effect, diolefine contained in feed stream and alkynes equal altitudes unsaturated hydrocarbons are selectively converted to corresponding monoolefine, thus reduce the height unsaturated hydrocarbons content easily generating coke in circulation heavy hydrocarbon.
In technical solution of the present invention, mainly form C according in preparing propylene from methanol reaction product
2~ C
4the characteristic distributions of hydrocarbon, adopts predepropanization separation process to carry out separation of olefins, first carries out C
3following olefin stream and C
4the fractionation by distillation of above olefin stream, and then carry out C
3the fractionation by distillation of following olefin stream, also can to C if needed
4fractionation by distillation is carried out in above logistics.Shortening distillation is arranged in the depropanizing tower of preparing propylene from methanol predepropanization separation process to be carried out.
In technical solution of the present invention, preparing propylene from methanol reaction pressure is 0.03 ~ 0.15MPaG, and preferred reaction pressure is 0.06 ~ 0.09MPaG; Temperature of reaction is 390 ~ 550 DEG C, and preferable reaction temperature is 450 ~ 500 DEG C.
In optimal technical scheme of the present invention, catalyst for producing propylene with methanol comprises Si-Al zeolite, SAPO molecular sieve or its mixture.Available Si-Al zeolite comprises ZSM-5, ZSM-11, chabazite, mordenite, clinoptilolite, erionite, ferrierite etc., and preferred Si-Al zeolite molecular sieve is ZSM-5 structure, and preferred SAPO molecular sieve is SAPO-34 structure.
In technical solution of the present invention, using preparing propylene from methanol reaction product through removing the charging of the olefin stream after water and most of oxygenatedchemicals as catalytic distillation, the water-content of olefin stream not higher than 50ppm, oxygenates level not higher than 3000ppm.
In optimal technical scheme of the present invention, hydroconversion reaction zone is by hydrogenation catalyst, or filler and hydrogenation catalyst, or column plate and hydrogenation catalyst, or filler, column plate and catalyst combination are formed.The mode of filler or column plate and catalyst combination is all react being uniformly distributed of contact between gas-liquid and liquid phase to improve hydrogenation catalyst, if hydrogenation catalyst own form and packed structures can meet above-mentioned requirements, then all can place hydrogenation catalyst in hydroconversion reaction zone.
In optimal technical scheme of the present invention, hydrogenation catalyst is at least one metal on porous support in nickel-loaded, palladium, platinum or rhodium or its oxide compound, can add the active constituents for suppressing stoping or eliminate the hydrogenation side reaction that complete stable hydrocarbon occurs in the catalyst.Preferable alloy or its oxide compound hydrogenation component at least major part are present in described hydrogenation catalyst with metallic state.Calculate based on metal, in catalyzer, the content of metal component counts 0.01 ~ 4wt% with catalyst weight percent, preferably 0.03 ~ 1.5wt%.The non-essential active constituents for suppressing of hydrogenation catalyst can be selected from copper, silver, gold, gallium, at least one metal of iridium or its oxide compound.Calculate based on metal, in catalyzer, the content of active constituents for suppressing is 0.001 ~ 2wt%, preferably 0.01 ~ 1.0wt%.When copper, silver etc. are active constituents for suppressing, at least major part is present in described hydrogenation catalyst with metallic state; And gallium, iridium etc. are when being active constituents for suppressing, then at least major part is present in described hydrogenation catalyst with metal oxide form.The porous carrier materials of hydrogenation catalyst can be any suitable material in hydrotreatment field.Porous carrier materials has 5 ~ 60m usually
2the surface-area of/g, comprises silicon-dioxide, silica gel, clay, silicate, refractory inorganic oxide, charcoal and rich Carbon Materials, spinel etc. or its composition material.Described hydrogenation catalyst can by the preparation of any known technology, to preferably include on porous carrier materials preliminary shaping, carrier order or side by side floods and/or spray hydrogenation metal component and non-essential active constituents for suppressing.
In optimal technical scheme of the present invention, filler is structured packing or random packing, and the array configuration of filler and catalyzer is alternately laminated, mixed heap, or filling surface floods and/or spraying catalyzer.
In optimal technical scheme of the present invention, the hydrogenation reaction pressure of catalytic distillation is 0.3 ~ 3.3MPa (G), is more preferably 1.0 ~ 2.8Mpa (G); Temperature of reaction is 35 ~ 150 DEG C, is more preferably 50 ~ 100 DEG C; Reaction weight space velocity is 0.1 ~ 400 hour
-1, be more preferably 1 ~ 150 hour
-1; In hydrogen and charging, the mol ratio of alkynes and diolefine is 0.7 ~ 10: 1, is more preferably mol ratio 1.1 ~ 5: 1.
In optimal technical scheme of the present invention, the oxygenatedchemicals in catalytic distillation feed stream at least comprises one or more C
1~ C
5ether, alcohol, aldehyde, ketone.Oxygenatedchemicals is the by product of preparing propylene from methanol reaction, and content is little, and the flow process through between reactor to catalytic distillation, major part is along with the by-products such as water remove.Enter oxygenates level in the logistics of catalytic distillation tower and, not higher than 3000ppm, be preferably 100 ~ 1500ppm.
In optimal technical scheme of the present invention, alkynes and di-olefins are the selectivity of monoolefine is 20 ~ 95%, is preferably 60 ~ 80%.The hydrogenation conversion of alkynes and diolefine is 50 ~ 100%, preferably 90 ~ 100%.Higher alkynes and diene hydrogenation transformation efficiency and be converted into the selectivity of monoolefine, the cycle of operation of preparing propylene from methanol reaction is extended and the prolongation of catalyst life all favourable, also can obtain higher propene yield simultaneously.
In optimal technical scheme of the present invention, in described hydroconversion reaction zone, space accounts for 20 ~ 80% of reaction zone volume, is preferably space and accounts for 40 ~ 70% of reaction zone volume.Suitable space should ensure effective duration of contact, and good liquid phase distribution, realizes alkynes and di-olefins; Reduce pressure drop again simultaneously as far as possible, reduce the energy consumption of catalytic distillation tower.
For preparing propylene from methanol, the middle and lower part distillation temperature of the depropanizing tower of its separation process can well be mated with hydrogenation catalyst temperature of reaction, and hydrogenation catalyst is contained in the middle and lower part of distillation tower, and the upper and lower of tower is respectively rectifying section and stripping section.Reaction product is gone out by fractionation by distillation at any time, is therefore conducive to improving reaction conversion ratio.On the other hand, the gas-liquid mutual-assistance hydrogenation reaction temperature of flowing is easy to realize stability contorting in tower, and reaction Heat of Formation be directly used in distillation can conserve energy.The light constituent of hydrogen with tower top in catalytic distillation tower of the remaining hydrogen of hydrogenation and reaction product self is separated, thus avoid fixed bed hydrogenation technique exist hydrogenation products in non-condensable gas on the impact of later separation flow process.Therefore, in the predepropanization separation process of preparing propylene from methanol, select the depropanizing tower being suitable for carrying out shortening to implement catalytic distillation technology technology, in operation, investment and propene yield etc., all can obtain better effect.Say from work angle, predepropanization shortening effectively can reduce the content of coking component, extend the cycle of operation of preparing propylene from methanol catalysts, and shortening temperature is easy to stability contorting and the less steam consumption of depropanizing tower simultaneously; From investment angle, save the investment of hydrogenation reaction system; Say from propene yield, propene yield can be increased to a certain extent.
The present invention is by adopting the predepropanization catalytic distillation hydrogenation technique of preparing propylene from methanol, effectively can reduce the alkynes in recycle hydrocarbons and diene content, not only extend MTP catalyst on-stream cycle time, and improve selectivity and the yield that MTP reacts propylene product, the MTP reactor cycle of operation can reach 700 ~ 1000 hours, be enhanced about more than once than prior art, the propene yield of the cycle of operation can improve 1 ~ 3wt% than prior art, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is document CN1989086A process flow diagram.
Fig. 2 is a kind of typical process of the inventive method predepropanization catalytic distillation hydrogenation technique.
In Fig. 1, Fig. 2,01 for comprising the raw material of methyl alcohol, and 02 is incoming mixture, and 03 is preparing propylene from methanol reactor, and 04 is reaction product, and 05 is quenching system, and 06 is heavy hydrocarbon, and 07 is gaseous stream after chilling, and 08 is the recycled process water, and 09 is efflux technology water, and 10 is C
2/ C
3knockout tower, 11 is C
2and following extraction logistics, 12 is C
2and following recycle stream, 13 is C
3and above logistics, 14 is C
3/ C
4knockout tower, 15 is C
3logistics, 16 is C
4and above logistics, 17 is C
4and above recycle stream, 18 is C
5/ C
6knockout tower, 19 is C
5and following logistics, 20 is C
6and above logistics, 21 is hydrogen make-up, and 22 is hydroconversion reaction zone, and 23 is depropanizing tower, and 24 is C
3and following logistics, 25 is outer row C
4~ C
5logistics, 26 is C
4~ C
5recycle stream.
In Fig. 1, methanol feedstock 01 and gaseous recycle process water 08, the C of gaseous state
2and following recycle stream 12, C
4and above recycle stream 17 mixes rear formation logistics 02, enter preparing propylene from methanol reactor 03, the logistics 04 that reaction produces is divided into gaseous stream 07 after chilling, liquid heavy hydrocarbon 06 and process water after quenching system 05 chilling, wherein except the efflux technology water 09 of part, all the other all mix with material benzenemethanol as dilution steam generation after vaporization.After chilling, gaseous stream 07 delivers to C after compression
2/ C
3knockout tower 10, a part of C obtained after being separated
2and following logistics circulation 12 mixes with material benzenemethanol after vaporization, all the other are as C
2and following extraction logistics 11; The C obtained after being separated
3and C is delivered in above logistics 13
3/ C
4knockout tower 14, is separated into C
3logistics 15 and C
4~ C
5logistics.C
4~ C
5in logistics, a part of C
4~ C
5logistics 17 circulates Returning reactor 03, and a part is as outer row C
4~ C
5logistics 16.
In Fig. 2, methanol feedstock 01 and gaseous recycle process water 08, the C of gaseous state
2and following recycle stream 12, C
4~ C
5recycle stream 26 mixes rear formation logistics 02, enter preparing propylene from methanol reactor 03, the logistics 04 that reaction produces is divided into gaseous stream 07 after chilling, liquid heavy hydrocarbon 06 and process water after quenching system 05 chilling, wherein except the efflux technology water 09 of part, all the other process waters 08 all mix with material benzenemethanol as dilution steam generation after vaporization.After chilling, gaseous stream 07 delivers to C after compression
5/ C
6knockout tower 18, the C of tower top after being separated
5and hydroconversion reaction zone 22 is gone in following logistics 19, the isolated C of tower reactor
6and the outer row of above logistics 20.Hydrogen make-up 21 adds under hydroconversion reaction zone 22, in hydroconversion reaction zone 22, carry out selective hydrogenation to alkynes contained in logistics 19 and diolefine.C
5and following logistics 19 is separated into C through depropanizing tower 23
3and following logistics 24 and C
4~ C
5logistics.C
4~ C
5in logistics, a part of C
4~ C
5logistics 26 circulates Returning reactor 03, and a part is as outer row C
4~ C
5logistics 25.C
3and C is delivered in following logistics 24
2/ C
3knockout tower 10, a part of C obtained after being separated
2and following logistics circulation 12 mixes with material benzenemethanol after vaporization, all the other are as C
2and following extraction logistics 11; The C obtained after being separated
3logistics 15 can be separated into propylene product and propane by-product further.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[comparative example 1]
Shown in Fig. 1, preparing propylene from methanol reaction adopts ZSM-5 catalyzer, and reaction pressure is 0.1MPa (G), and reaction temperature in is 450 DEG C, and dilution steam generation 08 is 0.9 with the mass flux ratio of charging 01, is separated the C obtained
2and following logistics and C
4and 85% circulation Returning reactor in above logistics.Feed stream 01 forms (% by weight): 20% methyl alcohol, 57.5% dme, 22.5% water; The C of circulation
4and above logistics 17 forms (% by weight) and is: 68.6%C
4(not comprising alkynes and diolefine), 23.5%C
5(not comprising alkynes and diolefine), 7.2%C
6and above (not comprising alkynes and diolefine), 0.7% alkynes and diolefine; The C of circulation
2and following logistics 12 forms (% by weight) and is: 65.7%C
2, 32.3% methane, 1.9% hydrogen, 0.1%CO
x.Enter the 0.3wt% that alkynes in the logistics of reactor and diolefine account for the total material not comprising water after feed stream 01 mixes with recycle stream, the propylene butt yield reached in the catalyzer of 500 ~ 600 hours online cycle is 65 ~ 68wt%.Press as 1.3MPa (G) at C3/C4 knockout tower tower, when reflux ratio is 1.0,0.35MPa (G) low-pressure steam that tower reactor reboiler consumes is that 4.6kg/kg distills charging.
[embodiment 1]
Shown in Fig. 2, preparing propylene from methanol reaction adopts ZSM-5 catalyzer, and reaction pressure is 0.1MPa (G), and reaction temperature in is 450 DEG C, and dilution steam generation 08 is 0.9 with the mass flux ratio of charging 01, is separated the C obtained
2and following logistics and C
4~ C
585% circulation Returning reactor in logistics; The tower pressure of depropanizing tower 23 is 1.5MPa (G), reflux ratio is 1.0, and hydrogenation catalyst reaction zone adopts nickel-base catalyst, and reaction zone temperature is 55 ~ 65 DEG C, add hydrogen 21 to ensure that the mol ratio of alkynes in hydrogen and charging 01 and diolefine is for 1.25, reaction weight space velocity is 15 hours
-1, containing 360ppm oxygenatedchemicals in charging 01, water is less than 1ppm.Feed stream 01 forms (% by weight): 20% methyl alcohol, 57.5% dme, 22.5% water; The C of circulation
4~ C
5logistics 26 forms (% by weight): 74.6%C
4(not comprising alkynes and diolefine), 25.4%C
5(not comprising alkynes and diolefine), 100ppm alkynes and diolefine; The C of circulation
2following logistics 12 forms (% by weight): 66.8%C
2, 32.9% methane, 0.2% hydrogen, 0.1%CO
x.Adopt the inventive method after hydrogenation reaction transforms, enter the 20ppm that alkynes in the logistics of reactor and diolefine account for the total material not comprising water after feed stream 01 mixes with recycle stream, the butt propylene average yield of the various products reached in the catalyzer online cycle of 100 hours, 500 hours, 1000 hours is as shown in table 1.According to experimental study, under equal load and reaction conditions, Catalyst Conversion reaches [comparative example 1] runs the equal level of deactivation of catalyzer of 500 hours, and the technique required time of the inventive method is about [comparative example 1] 1.5 times.0.35MPa (G) low-pressure steam that depropanizing tower tower reactor reboiler consumes is that 4.2kg/kg distills charging, reduces 8.7% than [comparative example 1].
[embodiment 2]
Shown in Fig. 2, preparing propylene from methanol reaction adopts ZSM-5 catalyzer, and reaction pressure is 0.1MPa (G), and reaction temperature in is 450 DEG C, and dilution steam generation 08 is 0.9 with the mass flux ratio of charging 01, is separated the C obtained
2and following logistics and C
4and 85% circulation Returning reactor in above logistics; The tower pressure of depropanizing tower 23 is 1.0MPa (G), hydrogenation catalyst reaction zone adopts nickel-base catalyst, reaction zone temperature is 60 ~ 70 DEG C, and add hydrogen 21 to ensure that the mol ratio of alkynes in hydrogen and charging 01 and diolefine is for 1.2, reaction weight space velocity is 12 hours
-1, containing 360ppm oxygenatedchemicals in charging 01, water is less than 1ppm.Feed stream 01 forms (% by weight): 20% methyl alcohol, 57.5% dme, 22.5% water; The C of circulation
4~ C
5logistics 26 forms (% by weight): 74.6%C
4(not comprising alkynes and diolefine), 25.4%C
5(not comprising alkynes and diolefine), 50ppm alkynes and diolefine; The C of circulation
2following logistics 12 forms (% by weight): 53.5%C
2, 43.5% methane, 0.7% hydrogen, 0.3%CO
x.Adopt the inventive method after hydrogenation reaction transforms, enter the 16ppm that alkynes in the logistics of reactor and diolefine account for the total material not comprising water after feed stream 01 mixes with recycle stream, the butt propylene average yield of the various products reached in the catalyzer online cycle of 100 hours, 500 hours, 1000 hours is as shown in table 1.According to experimental study, under equal load and reaction conditions, Catalyst Conversion reaches [comparative example 1] runs the equal level of deactivation of catalyzer of 500 hours, and the technique required time of the inventive method is about [comparative example 1] 2.0 times.0.35MPa (G) low-pressure steam that depropanizing tower tower reactor reboiler consumes is that 3.8kg/kg distills charging, reduces 7.3% than [comparative example 1].
Table 1
| Reaction times | 100 hours | 300 hours | 500 hours | 1000 hours |
| Embodiment 1 | 73.4wt％ | 73.9wt％ | 73.6wt％ | 72.6wt％ |
| Embodiment 2 | 73.5wt％ | 73.8wt％ | 74.2wt％ | 73.1wt％ |
| Comparative example 1 | 67wt％ | 68wt％ | 66wt％ | Inactivation |
As can be seen from Table 1, adopt method of the present invention, propene yield can reach 74%, and improve 5 ~ 6wt% than existing technique, have not yet to see obvious inactivation through 500 hours catalyzer, catalyst on-stream cycle time can reach 700 ~ 1000 hours, improves 1 times than existing technique.
Claims (3)
1. a method for preparing propylene from methanol, comprising:
A) raw material I comprising methyl alcohol enters in preparing propylene from methanol reactor and contacts with catalyst for producing propylene with methanol, and reaction generates the logistics II comprising propylene;
B) logistics II obtains gaseous stream III after chilling, liquid heavy hydrocarbon and process water through quenching system, and liquid heavy hydrocarbon is discharged out-of-bounds, and at least 10 % by weight of process water is back to reactor;
C) logistics III enters the top of depropanizing tower hydroconversion reaction zone, obtains C at tower top
3and following logistics IV, obtain C at the bottom of tower
4and above logistics V, at least 30 % by weight of logistics V is back to reactor;
D) logistics IV enters C
2/ C
3knockout tower, obtains C at tower top
2and following logistics VI, at least 30 % by weight of logistics VI is back to reactor, obtains C at the bottom of tower
3cut;
Wherein, in hydroconversion reaction zone, space accounts for 20 ~ 80% of reaction zone volume, and hydrogenation catalyst is contained in the middle and lower part of depropanizing tower, and the upper and lower of tower is respectively rectifying section and stripping section; Hydroconversion reaction zone is by hydrogenation catalyst, or filler and hydrogenation catalyst, or column plate and hydrogenation catalyst, or filler, column plate and catalyst combination are formed;
Hydroconversion reaction zone reaction pressure is 0.3 ~ 3.3MPaG, and temperature of reaction is 35 ~ 150 DEG C, and reaction weight space velocity is 0.1 ~ 400 hour
-1, in hydrogen and charging, the mol ratio of alkynes and diolefine is 0.7 ~ 10:1; Hydrogenation catalyst is at least one metal on porous support in nickel-loaded, palladium, platinum or rhodium or its oxide compound, calculate based on metal, in catalyzer, the content of metal component counts 0.01 ~ 4 % by weight with catalyst weight percent, and porous carrier materials has 5 ~ 60m
2the surface-area of/g, comprises silicon-dioxide, silica gel, clay, silicate, refractory inorganic oxide, charcoal and rich Carbon Materials, spinel or its composition material; The active constituents for suppressing of hydrogenation catalyst is selected from copper, silver, gold, gallium, at least one metal of iridium or its oxide compound; Calculate based on metal, in catalyzer, the content of active constituents for suppressing is 0.001 ~ 2wt%.
2. the method for preparing propylene from methanol according to claim 1, it is characterized in that preparing propylene from methanol reactor reaction pressure is 0.03 ~ 0.15MPaG, temperature of reaction is 390 ~ 550 DEG C, and catalyzer is selected from ZSM zeolite molecular sieve, SAPO molecular sieve or its mixture.
3. the method for preparing propylene from methanol according to claim 1, it is characterized in that alkynes and di-olefins in described hydroconversion reaction zone be the selectivity of monoolefine are 20 ~ 95%, transformation efficiency is 50 ~ 100%.
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| CN106732201B (en) * | 2017-01-05 | 2019-11-29 | 中石化上海工程有限公司 | Catalyst for Oxidative Coupling of Methane reactor |
| CN110041157B (en) * | 2019-05-10 | 2022-07-01 | 国家能源投资集团有限责任公司 | Method for improving yield of propylene prepared from methanol and prolonging service life of catalyst |
| CN113512013B (en) * | 2021-06-30 | 2023-09-05 | 中国石油化工股份有限公司 | System and method for preparing propylene oxide from large-scale industrial methanol |
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| CN1989086A (en) * | 2004-06-25 | 2007-06-27 | 环球油品公司 | Conversion of oxygenate to propylene using moving bed technology |
| CN101062483A (en) * | 2006-04-27 | 2007-10-31 | 中国石油化工股份有限公司 | Novel selective hydrogenation catalyst and preparation method thereof |
| CN101367697A (en) * | 2008-10-15 | 2009-02-18 | 上海惠生化工工程有限公司 | Separation method for light hydrocarbon products in MTO/MTP reaction products |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1989086A (en) * | 2004-06-25 | 2007-06-27 | 环球油品公司 | Conversion of oxygenate to propylene using moving bed technology |
| CN101062483A (en) * | 2006-04-27 | 2007-10-31 | 中国石油化工股份有限公司 | Novel selective hydrogenation catalyst and preparation method thereof |
| CN101367697A (en) * | 2008-10-15 | 2009-02-18 | 上海惠生化工工程有限公司 | Separation method for light hydrocarbon products in MTO/MTP reaction products |
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