CN105985801B - One kind promotes catalysis drying gas gasoline and liquefaction gas method - Google Patents
One kind promotes catalysis drying gas gasoline and liquefaction gas method Download PDFInfo
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Abstract
The present invention provides a kind of promotion catalysis drying gas gasoline and liquefaction gas method, belongs to petrochemical industry.Follow the steps below：(1) rare earth ZSM5/ZSM11 cocrystallization zeolites are mixed with alumina binder, extrusion, dried, required catalyst is made in roasting, ion exchange and steam treatment；(2) catalyst prepared is applied to catalysis drying gas and the co-feeding aromatisation of water vapour prepares gasoline and liquefied gas.The advantage of the invention is that：Compared with only aromatisation containing catalysis drying gas, liquefied gas and yield of gasoline and Aromatic Hydrocarbon in Gasoline selectivity are higher on catalysis drying gas and the co-feeding catalyst of water vapour.
Description
Technical field
The invention belongs to petrochemical industry, and in particular to one kind promotes catalysis drying gas gasoline and liquefaction gas method.
Background technology
Catalytic cracked dry gas is the tail gas of refinery's by-product, wherein containing ethene 12-25% (volume fraction).At present, China
Catalytic cracking unit scale occupies the ethene considerable amount in second place of the world, dry gas.Generally burnt dry gas as fuel gas
Fall, both cause atmosphere pollution, waste the ethene resource of preciousness；Ethylbenzene manufactured from ethylene is that simple and effective dry gas is straight in dry gas
Connect and utilize technology, it is commonplace in the application of China, but can be supplied and limited by benzene.If passing through ethene in catalytic cracked dry gas
The reaction such as overlapping, cyclisation, dehydrogenation, hydrogen migration and isomerization is gone through, high-octane gasoline and liquefied gas is produced, will be catalytic cracking
Dry-gas recovery utilizes the expansion of technology, can not only reach the purpose that high value added product is produced using limited resources, alleviationization
Work increases Business Economic Benefit the problem of there is lack of raw materials；Meet environment-friendly principle simultaneously, energy-saving and emission-reduction are optimized the environment, had
Significant social benefit.
M.P.Rosynek (Ping Qiu, J.H.Lunsford, M.P.Rosynek.Catal.Lett, 52 (1998) 37~
Etc. 42) dilute ethene (3%) is reported in high temperature (500-550 DEG C) aromatization performance on Ga/ZSM-5 molecular sieves, only
0.5wt% Ga ensures that catalyst has good aromatics yield, and aromatic hydrocarbons generation is a complex process, is related to polymerization, different
Structure, cracking and cyclisation, the activated centre of reaction isGa in acid, framework of molecular sieve3+With molecular sieve pore passage and outside
The Ga of surface area2O3Promote the dehydrogenation of polymer and cyclisation product.
V.R.Choudhary(V.R.Choudhary,P.Devadas,S.Banerjee,
A.K.Kinage.Micro.Meso.Mate, 47 (2001) 253~267) etc. compare first on H-ZSM-5 and H-GaAlMFI
Aromatisation situation, as a result show, H-GaAlMFI it is upper activity have obvious superiority, strong acid be reaction activated centre, second
The ratio direct correlation of the conversion ratio of alkene and the yield of aromatic hydrocarbons and non-skeleton Ga/ strong acid, at 1, the yield of aromatic hydrocarbons is optimal；Investigate
Temperature and air speed are to dilute ethene (5%VC on H-GaAlMFI2H4/ 95%VN2) Aromatization Activity influence, selectivity of product,
Special aromatic hydrocarbons, propylene, C4Hydrocarbon is influenceed by air speed and temperature, C8Arenes selectivity is closely related with arene content, and aromatic hydrocarbons is mainly
Ortho position and paraxylene, while proposing a reaction path.
King hall medium (Wang Dianzhong, what ring member petroleum refining and chemical industry, 26 (1995) 59~63) to through nitrogen dilute it is dilute
Ethene oligomerization on ZSM-5 molecular sieve is investigated, and is as a result shown, in 0.7MPa, and ethene air speed is 1h-1Under conditions of
Reaction, generation gasoline is in the majority at 350 DEG C, and it is in the majority that temperature is less than the isobutene generated at 300 DEG C.Split using the catalysis of dilute vinyl analog
Change the H in dry gas, dry gas2And H2O ethylene reaction result on ZSM-5 molecular sieve is shown (Wang Dianzhong, what ring member petroleum refinings and
Chemical industry, 26 (1995) 15~18), work as H2In the presence of, ethane recovery increase, yield of gasoline declines, and H2O can suppress H2No
Profit influence, and the carbon deposition rate of conversion of ethylene and reduction catalyst can be improved.
United States Patent (USP) (USP 4150062) discloses a kind of method for improving low-carbon alkene generation gasoline fraction, and raw material is
C1-C4 hydrocarbon and H2S, catalyst is ZSM-5, ZSM-11, ZSM-12, ZSM-35, one or more of in ZSM-38, and water/alkene is former
It is co-feeding, the ratio with only olefin-containing raw material under the conditions of 0.5~15 to expect mol ratio, and alkene in raw material can be promoted on catalyst to turn
Turn to high-knock rating gasoline cut.
Chen Xiang etc. (Chen Xiang, Li Jun, a nanmu Chemical Industry in Guangzhou, 40 (2012) 114~116) has highlighted ZSM-5 molecular sieve
The commerical test of ethene technique for preparing gasoline and commercial Application situation in upper catalysis drying gas.By the checking of industrial experiment, catalysis is split
It is practicable to change dry gas technique for preparing gasoline, and conversion of ethylene is higher than 90%, and catalyst single pass life is more than 45 days, product gas
Olefin(e) centent is significantly lower than unstrpped gas olefin(e) centent in body, and product gasoline can be used as preferable gasoline blending component.
Chinese patent (CN.201410742632.5) discloses a kind of system of the ZSM11 molecular sieve catalysts of binder free
Preparation Method.The catalyst of preparation is applied to ethene aromatisation in catalysis drying gas and prepares gasoline and liquefied gas, viscous with only silicon oxide-containing
The molecular sieve catalyst of knot agent is compared, and conversion of ethylene is higher on Adhesive-free Molecular Sieve catalyst, and stability is more preferable.
With liquefied gas produce gasoline technology be rapidly developed in recent years, but catalysis drying gas utilization much
Liquefied gas is lagged behind, the molecular sieve that current dry gas gasoline and liquefied gas are reported is only ZSM-5 and ZSM-11, rare earth-ZSM5/
The reaction is not yet reported that on ZSM11 cocrystallized zeolite catalysts.
The content of the invention
The present invention provides catalysis drying gas gasoline and liquid on a kind of raising rare earth-ZSM5/ZSM11 cocrystallized zeolite catalysts
Change gas yield method.Compared with only aromatisation containing catalysis drying gas, liquefied on catalysis drying gas and the co-feeding catalyst of water vapour
Gas and yield of gasoline and Aromatic Hydrocarbon in Gasoline selectivity are higher.
The technical problems to be solved by the invention are to be hydrogenated to ethane by adding water vapour one side ethene suppressing, separately
On the one hand the carbon distribution or carbon distribution presoma of catalyst are suppressed, so as to improve ethylene synthesis gasoline and liquefied gas contribution.
A kind of promotion catalysis drying gas gasoline and liquefaction gas method of the invention, are followed the steps below：
(1) rare earth-ZSM5/ZSM11 cocrystallization zeolites are mixed with alumina binder, extrusion, dried, roasting, ion
Exchange and required catalyst is made in steam treatment；
(2) catalyst prepared is applied to catalysis drying gas and the co-feeding aromatisation of water vapour prepares gasoline and liquefaction
Gas.
The amount of aluminum oxide is that rare earth-ZSM5/ZSM11 cocrystallization zeolites are mixed with alumina binder in the step (1)
The 10-50% of thing weight；
The alumina source is in boehmite, aluminum sulfate, aluminum nitrate or its mixture.
In the step (1), drying temperature is 120~150 DEG C；Sintering temperature be 500~650 DEG C, roasting time be 3~
7h；Solution used in ion exchange is hydrochloric acid or ammonium nitrate solution, and its concentration is 0.2-0.8mol/L；The temperature of ion exchange is
60-80℃；Steam treatment temperature is 350-650 DEG C, and the steam treatment time is 2-6h.
The catalyst prepared is applied to the step (2) into catalysis drying gas and the co-feeding aromatisation of water vapour prepares gasoline
And liquefied gas, reaction temperature is 280-500 DEG C, and pressure is that weight ethylene air speed is 0.1- in 0.1-3.0MPa, catalysis drying gas
1.5h-1。
The catalysis drying gas 10-60%v containing ethene, H2S 100-5000ppm, COx 1.0-5.0%v, oxygen 0.1-1.5%
V, water is 1000-4000ppm.
The water vapour derives from water, methanol, ethanol or its mixture, H2O (gas)/catalysis drying gas=0.05%v-
15%v.
The present invention preferred embodiment be：It will mix and the good rare earth-ZSM5/ZSM11 cocrystallized zeolite catalysts of extrusion, in
550 DEG C of roasting 2h, are exchanged in 60-80 DEG C with 0.2-0.8mol/L hydrochloric acid or ammonium nitrate solution, washed, 500-650 after drying
DEG C roasting 3-7h, 350-650 DEG C of steam treatment 2-6h, H- type rare earth-ZSM5/ZSM11 cocrystallized zeolite catalysts are made.
One of unstripped gas that the present invention is used is the dry gas (being referred to as catalysis drying gas) of catalytic cracking or catalytic pyrolysis, catalysis
Dry gas is not required to purification, such as not desulfurization, be not dehydrated, not deoxidation, not de- COx etc., catalysis drying gas 10-60%v containing ethene, H2S 100-
5000ppm, COx 1.0-5.0%v, oxygen 0.1-1.5%v, water is 1000-4000ppm.
Another unstripped gas that the present invention is used is water vapour, from water, methanol, ethanol or its mixture, H2O(gas)/
Catalysis drying gas=0.05%v-15%v.
, can be ethene in catalysis drying gas through aromatization using the co-feeding method of catalysis drying gas of the present invention and water vapour
Change reaction and obtain gasoline in high yield and liquefied gas.Compared with only aromatisation containing catalysis drying gas, catalysis drying gas and water vapour enter altogether
Liquefied gas and yield of gasoline and Aromatic Hydrocarbon in Gasoline selectivity are higher on the catalyst of material.
Rare earth-ZSM5/ZSM11 cocrystallization zeolites are different from the mechanical impurity of rare earth, ZSM5 and ZSM11.The cocrystallization
Zeolite is to inlay rare earth while cocrystallization ZSM5/ZSM11 zeolites (mechanical impurity for being different from ZSM and ZSM11) is synthesized
It has been embedded into what is formed in cocrystallization ZSM5/ZSM11 zeolitic frameworks.The zeolite molecular sieve have good acid hydrothermal stability and
Anti- impurity pollution capacity (see Chinese patent CN1137022A and the Republic of China eight pseudo-ginseng O of patent O bis-).This is for being related to
There is greatly industrial Practical significance for the catalytic process of hydro-thermal process (regeneration of such as catalyst).
Embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
Comparative example 1
10 grams of rare earth-ZSM5 zeolites (rare earth accounts for the heavy % of the zeolite weight content 3.2) are weighed, 5.56 gram 77% is added
After the boehmite mixing of (weight) aluminum oxide, extrusion molding, through 120 DEG C of drying, is used after 550 DEG C of roasting 2h at 80 DEG C
0.8mol/L ammonium nitrate solution is exchanged 3 times, is washed 2 times, 120 DEG C of dryings, 540 DEG C of roasting 3h, then 550 DEG C of processing of water vapour
2h, gained catalyst is denoted as Cat-A.
Comparative example 2
10 grams of rare earth-ZSM11 cocrystallization zeolites (rare earth accounts for the heavy % of the zeolite weight content 3.2) are weighed, 5.56 are added
After the boehmite mixing of gram 77% (weight) aluminum oxide, extrusion molding, through 120 DEG C of drying, after 550 DEG C of roasting 2h at 80 DEG C
Exchanged 3 times, washed 2 times, 120 DEG C of dryings with 0.8mol/L ammonium nitrate solution, 540 DEG C of roasting 3h, then at 550 DEG C of water vapour
2h is managed, gained catalyst is denoted as Cat-B.
Embodiment 1
Weighing 10 grams of the weight %ZSM5/50 weights of rare earth -50 %ZSM11 cocrystallization zeolites, (rare earth accounts for the cocrystallization zeolite weight
Measure the heavy % of content 3.2), after the boehmite mixing for adding 5.56 gram of 77% (weight) aluminum oxide, extrusion molding, through 120 DEG C of bakings
It is dry, exchanged 3 times, washed 2 times, 120 DEG C of dryings, 540 DEG C with 0.8mol/L ammonium nitrate solution at 80 DEG C after 550 DEG C of roasting 2h
3h is calcined, then 550 DEG C of processing 2h of water vapour, gained catalyst is denoted as Cat-C.
Embodiment 2
Weighing the 10 grams of weight %ZSM5/70 weight %ZSM11 of rare earth -30 cocrystallization zeolites, (rare earth accounts for the cocrystallization zeolite weight
The heavy % of content 1.2), add after 3.8 grams of aluminum nitrate mixing, extrusion molding, through 120 DEG C of drying, 550 DEG C are calcined after 2h at 80 DEG C
Exchanged 3 times, washed 2 times, 120 DEG C of dryings with 0.3mol/L ammonium nitrate solution, 570 DEG C of roasting 4h, then at 625 DEG C of water vapour
3h is managed, gained catalyst is denoted as Cat-D.
Embodiment 3
Weighing the 10 grams of weight %ZSM5/50 weight %ZSM11 of rare earth -50 cocrystallization zeolites, (rare earth accounts for the cocrystallization zeolite weight
The heavy % of content 5.2), add 3.8 grams of aluminum nitrates and 20.0 grams of aluminum sulfate (Al2(SO4)3.18H2O after) mixing, extrusion molding, warp
Exchanged 2 times, washed 2 times, 140 DEG C of dryings with 0.4mol/L hydrochloric acid solution at 65 DEG C after 120 DEG C of drying, 550 DEG C of roasting 2h,
550 DEG C are calcined 3h, then 400 DEG C of processing 5h of water vapour, and gained catalyst is denoted as Cat-E.
Embodiment 4
Weighing 10 grams of the weight %ZSM5/90 weights of rare earth -10 %ZSM11 cocrystallization zeolites, (rare earth accounts for the cocrystallization zeolite weight
Measure content 2.5 heavy %), add 5.56 gram of 77% (weight) aluminum oxide boehmite and with 20.0 grams of Al2(SO4)3.18H2O is mixed
After conjunction, extrusion molding, through 120 DEG C of drying, is exchanged 2 times after 550 DEG C of roasting 2h at 70 DEG C with 0.5mol/L ammonium nitrate solution,
Washing 2 times, 140 DEG C of dryings, 600 DEG C are calcined 4h, then 600 DEG C of processing 2h of water vapour, and gained catalyst is denoted as Cat-F.
Comparative example 1~2 and the reaction evaluating of embodiment 1~4
The catalyst of comparative example 1 and the gained of embodiment 1~4 is respectively placed in internal diameter anti-for the fixed bed that 24mm continuously flows
Answer and catalyst performance evaluation is carried out in device, the loadings of catalyst are 5g, in N2500 DEG C of activation 1h are warming up under atmosphere, then
In N2Atmosphere drops to reaction temperature, and raw material is catalysis drying gas and water vapour.Reacted product is cooled down into promoting the circulation of qi through cooler
Liquid is separated.Gas and product liquid are constituted with the type chromatographics of Varian 3800, and analysis uses PONA capillaries
Post, hydrogen flame detector.
The composition of unstripped gas as shown in table 1, aromatization condition and the results are shown in Table 2.From Table 2, it can be seen that catalysis
Dry gas and water vapour co-feeding catalyst Cat-A and Cat-B gasoline and yield of liquefied gas are significantly lower than same reaction conditions
Lower Cat-C parameter；The conversion ratio of ethene liquefied gas in 96.6%, the product of ethene conversion on the Cat-C of aqueous (0.8%)
Arenes selectivity 32.4% in yield 34.0%, gasoline liquid yield 56.3%, liquid, and the only catalyst containing catalysis drying gas
Analog value on Cat-C is respectively 90.6%, 19.0%, 21.3% and 28.8%.Under the reaction condition investigated, Cat-C
The conversion ratio of the upper ethene of~Cat-F is more than 90%, yield of liquefied gas in the product of ethene conversion>34%, gasoline liquid yield>
50%, arenes selectivity in liquid>30%.
The composition (v%) of the unstripped gas of table 1
The catalytic reaction evaluation result of the various catalyst of table 2 (reaction time is 50h)
*：Water derives from methanol, ethanol, water and alcohol mixture
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (6)
1. one kind promotes catalysis drying gas gasoline and liquefaction gas method, it is characterised in that follow the steps below：
(1) rare earth-ZSM5/ZSM11 cocrystallization zeolites are mixed with alumina binder, extrusion, dried, roasting, ion exchange
Catalyst needed for being made with steam treatment；
(2) catalyst prepared is applied to catalysis drying gas and the co-feeding aromatisation of water vapour prepares gasoline and liquefied gas.
2. promote catalysis drying gas gasoline and liquefaction gas method according to a kind of described in claim 1, it is characterised in that：The step
(1) amount of aluminum oxide is the 10-50% of rare earth-ZSM5/ZSM11 cocrystallization zeolites and alumina binder mixture weight in；
The alumina source is in boehmite, aluminum sulfate, aluminum nitrate or its mixture.
3. promote catalysis drying gas gasoline and liquefaction gas method according to a kind of described in claim 1, it is characterised in that：The step
(1) in, drying temperature is 120~150 DEG C；Sintering temperature is 500~650 DEG C, and roasting time is 3~7h；Used in ion exchange
Solution be hydrochloric acid or ammonium nitrate solution, its concentration be 0.2-0.8mol/L；The temperature of ion exchange is 60-80 DEG C；Water vapour
Treatment temperature is 350-650 DEG C, and the steam treatment time is 2-6h.
4. promote catalysis drying gas gasoline and liquefaction gas method according to a kind of described in claim 1, it is characterised in that：Step (2)
The catalyst prepared is applied to catalysis drying gas and the co-feeding aromatisation of water vapour prepares gasoline and liquefied gas, reaction temperature is
280-500 DEG C, pressure is that weight ethylene air speed is 0.1-1.5h in 0.1-3.0MPa, catalysis drying gas-1。
5. promote catalysis drying gas gasoline and liquefaction gas method according to claim 4 one kind, it is characterised in that：The catalysis drying gas
Percent by volume containing ethene is 10-60%, H2S 100-5000ppm, COx percent by volume are 1.0-5.0%, the body of oxygen
Product percentage is 0.1-1.5%, and water is 1000-4000ppm.
6. promote catalysis drying gas gasoline and liquefaction gas method according to claim 4 one kind, it is characterised in that：The water vapour comes
Water, methanol, ethanol or its mixture are come from, the volume ratio of water vapour/catalysis drying gas is=0.05%-15%.
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| CN103357430A (en) * | 2012-03-30 | 2013-10-23 | 中国科学院大连化学物理研究所 | Cocrystallization molecular sieve catalyst for aromatization, as well as preparation method and application thereof |
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| CN103357430A (en) * | 2012-03-30 | 2013-10-23 | 中国科学院大连化学物理研究所 | Cocrystallization molecular sieve catalyst for aromatization, as well as preparation method and application thereof |
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