CN105728017B - A kind of preparation and application of 1 molecular sieve catalyst of binderless ZSM-11 - Google Patents
A kind of preparation and application of 1 molecular sieve catalyst of binderless ZSM-11 Download PDFInfo
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Abstract
The purpose of the present invention is to provide a kind of preparation method and application of the ZSM11 molecular sieve catalysts of binder free, the specific steps are：The mixture that weight content is formed for 10~50% silica binders with ZSM11 molecules original powder, in the aqueous solution or steam containing alkyl diamine and/or halogenation organic amine, hydrothermal treatment wherein will be converted into ZSM11 molecular sieves by binding agent silica, and 1 catalyst of monoblock type binderless ZSM-11 is formed with original ZSM11 molecular sieves；The binderless ZSM-11 1 prepared is by ion exchange, and dry, required catalyst is made in roasting, steam treatment.Catalyst prepared by the present invention is applied to ethylene aromatisation in catalysis drying gas and prepares gasoline and liquefied gas.The advantage of the invention is that：Compared with the molecular sieve catalyst for containing only silica binder, conversion of ethylene higher on Adhesive-free Molecular Sieve catalyst, stability is more preferable.
Description
Technical field
The invention belongs to petrochemical industries, and in particular to a kind of preparation side of 1 molecular sieve catalyst of binderless ZSM-11
Method and application.
Background technology
Catalytic cracked dry gas is the tail gas of refinery's by-product, wherein containing ethylene 12-25% (volume fraction).At present, China
Catalytic cracking unit scale occupies second place of the world, the ethylene considerable amount in dry gas.Usually burnt dry gas as fuel gas
Fall, both cause atmosphere pollution, waste valuable ethylene resource；Ethylbenzene manufactured from ethylene is that simple and effective dry gas is straight in dry gas
Utilization technology is connect, the application in China is commonplace, but can be supplied and be limited by benzene.If pass through ethylene in catalytic cracked dry gas
The reactions such as overlapping, cyclisation, dehydrogenation, hydrogen migration and isomerization are gone through, produce high-octane gasoline and liquefied gas, will be catalytic cracking
Dry-gas recovery utilizes the expansion of technology, can not only achieve the purpose that produce high value added product, alleviationization using limited resources
Work the problem of there is lack of raw materials, increase Business Economic Benefit；Meet environmental-friendly principle simultaneously, energy-saving and emission-reduction are optimized the environment, and are had
Significant social benefit.
M.P.Rosynek (Ping Qiu, J.H.Lunsford, M.P.Rosynek.Catal.Lett, 52 (1998) 37~
Etc. 42) dilute ethylene (3%) is reported in high temperature (500-550 DEG C) aromatization performance on Ga/ZSM-5 molecular sieves, only
The Ga of 0.5wt% ensures that catalyst has good aromatics yield, and aromatic hydrocarbons generation is a complex process, is related to polymerizeing, different
Structure, cracking and cyclisation, the activated centre of reaction isAcid, the Ga in framework of molecular sieve3+With molecular sieve pore passage and appearance
The Ga of 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 on H-ZSM-5 and H-GaAlMFI first
Aromatisation situation, the results showed that, H-GaAlMFI it is upper activity have apparent superiority, strong acid be reaction activated centre, second
The conversion ratio of alkene and the yield of aromatic hydrocarbons and the ratio of non-skeleton Ga/ strong acid are directly linked, and at 1, the yield of aromatic hydrocarbons is best；It investigates
Temperature and air speed are to ethylene (5%C dilute on H-GaAlMFI2H4/ 95%N2) Aromatization Activity influence, selectivity of product is special
Other aromatic hydrocarbons, propylene, C4Hydrocarbon is influenced by air speed and temperature, C8Arenes selectivity is closely related with arene content, and aromatic hydrocarbons is mainly neighbour
Position and paraxylene, while propose a reaction path.
King hall medium (Wang Dianzhong, what ring member petroleum refining and chemical industry, 26 (1995) 59~63) is to diluted dilute through nitrogen
Ethylene oligomerization on ZSM-5 molecular sieve is investigated, the results showed that, in 0.7MPa, ethylene 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.It is split using the catalysis of dilute vinyl analog
Change dry gas, the H in dry gas2And H2O to ethylene reaction on ZSM-5 molecular sieve the result shows that (Wang Dianzhong, what ring member petroleum refinings and
Chemical industry, 26 (1995) 15~18), work as H2In the presence of, ethane recovery increases, and yield of gasoline declines, and H2O can inhibit H2No
Profit influences, and can improve conversion of ethylene and reduce the carbon deposition rate of catalyst.
Chen Xiang etc. (Chen Xiang, Li Jun, nanmu Chemical Industry in Guangzhou, 40 (2012) 114~116) has highlighted ZSM-5 molecular sieve
The commerical test of ethylene technique for preparing gasoline and commercial Application situation in upper catalysis drying gas.By the verification 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 ideal gasoline blending component.
It had been rapidly developed with the technology of liquefied gas production gasoline in recent years, but the utilization of catalysis drying gas is much
Liquefied gas is lagged behind, the molecular sieve that dry gas gasoline and liquefied gas are reported at present is only ZSM-5, -11 molecule of binderless ZSM-5
The reaction is not yet reported that on sieve catalyst.
The molecular sieve usually synthesized is in superfine powdered, only several microns, but for a kind of catalyst of commercial Application
For, it is desirable that catalyst has certain shape and mechanical strength, if not, since the pressure of load can be made in application
Into many undesirable consequences or even it is forced to stop.Tiny molecular sieve powder in order to meet application request, generally require with
Inorganic binder forms molecular sieve catalyst of different shapes together.In order to ensure that molecular sieve catalyst of different shapes has phase
The mechanical strength answered, binding agent are essential shaping assistants.Inert binding agent material is added in powdered molecular sieve catalyst
Material can make shaping of catalyst, so as to improve its in commercial Application required mechanical strength (R.Jasra, N.Choudary,
S.Bhat, Sep.Sci.Tech, 26 (1991) 885~930).Although binding agent relative inertness, after being mixed with catalyst itself
The proton exchange performance of molecular sieve can be adjusted, while the physical duct for occupying molecular sieve in forming process so that change its hole
Porosity (F.Dorado, R.Romero, P.Appl.Cata.A, 236 (2002) 235~243).Binding agent at present
Mostly using silica and aluminium oxide, aluminium atom, which enters framework of molecular sieve, wherein in alumina binder increases molecular sieve acid amount
(C.D.Chang,S.D.Hellring,J.N.Miale,K.D.Schmitt,P.Brigandi,E.Wu,
J.Chem.Soc.Faraday Trans, 81 (1985) 2215~2224)；And silica binder then reduces its acid amount
(X.Wu, A.Alkhawaldeh, R.Anthony, Stud.Surf.Sci.Catal, 143 (2000) 217-225), intensity decline.
If silica binder is converted into molecular sieve, formed together with original molecular sieve with definite shape, size and machinery
The catalysis material of intensity, i.e. Adhesive-free Molecular Sieve catalyst can fill under conditions of catalytic mechanical intensity and acid amount is ensured
The reactivity worth of catalyst is waved in distribution.The method of synthesis bindless molecular sieve has a liquid-solid phase conversion method, gas-solid phase inversion and
Assembled formation method etc., what success synthesized has MFI, BEA, MEL, FAU and FER etc. serial.- 11 molecular sieve of binderless ZSM-5 at present
The report of catalyst synthesis is few.
Invention content
The purpose of the present invention is to provide a kind of preparation method and application of 1 molecular sieve catalyst of binderless ZSM-11, with
It contains only silica binder molecular sieve catalyst to compare, the Adhesive-free Molecular Sieve catalyst prepared by the method for the invention
Upper conversion of ethylene higher, the stability of catalyst can be also obviously improved.
The technical problems to be solved by the invention are binding agents present in previous molecular sieve catalyst, can reduce unit matter
The active ingredient in catalyst is measured, reactant, the diffusion of product in the catalyst is hindered, reduces reactivity and the production of catalyst
The problem of giving birth to more by-product, provides a kind of preparation method of 1 molecular sieve catalyst of binderless ZSM-11.The preparation method has
Molecular sieve catalyst crystallinity height is obtained, without binding agent, the advantages of preparation flow is simple.
The present invention provides a kind of preparation method of 1 molecular sieve catalyst of binderless ZSM-11, specific method step is：
(1) ZSM11 molecular sieve powders and amorphous silica binding agent (preferably are selected from Ludox, waterglass or it is mixed
Close object) mixing, the weight percentage of silica is 10~50% (preferably 20~40%) wherein in silica binder；
After shaping and drying, in the water containing alkyl diamine and/or halogenation organic amine (preferably 1,6- hexamethylene diamines and/or four butyl bromation amine)
In solution or steam, hydrothermal treatment is converted into 1 molecular sieve of binderless ZSM-11, and wherein crystallization temperature is (excellent for 100~200 DEG C
Select 140~180 DEG C), crystallization time is 10~100 hours (preferably 24~72 hours).
(2) 1 molecular sieve of binderless ZSM-11 prepared is passed through into ion exchange, dry, roasting, steam treatment, system
The ZSM11 molecular sieve catalysts of binder free are obtained, preferred embodiment is：The binderless ZSM-11 1 that will be prepared, washing and drying after
550 DEG C of roasting 2h are exchanged, washing, 500-650 after drying with the hydrochloric acid or ammonium nitrate solution of 0.2-0.8mol/L in 60-80 DEG C
DEG C roasting 3-7h, 350-650 DEG C of steam treatment 2-6h, 1 molecular sieve catalyst of H- types binderless ZSM-11 is made.
To sum up, catalyst provided by the invention is by ZSM11 molecular sieve powders and amorphous silica binding agent
Mixing, shaping and drying are converted into 1 molecular sieve of binderless ZSM-11 after the water from steam heat treatment containing amine, are then handed over through ion
It changes, dry, required catalyst is made in roasting and steam treatment.The catalyst can be applied to ethylene aromatization metaplasia in catalysis drying gas
Into gasoline and liquefied gas.
Dry gas (be referred to as catalysis drying gas) of the unstripped gas that the present invention uses for catalytic cracking or catalytic pyrolysis, catalysis drying gas
It is not required to purify, such as not desulfurization, is not dehydrated, not deoxidation, does not take off COx etc., catalysis drying gas 10-60%v containing ethylene, H2S 100-
5000ppm, COx 1.0-5.0%v, oxygen 0.1-1.5%v, water 1000-4000ppm.
Ethylene in catalysis drying gas, can be obtained height by the catalyst prepared using the method for the invention through aromatization
Yield gasoline and liquefied gas.Compared with the molecular sieve catalyst for containing only silica binder, 1 molecular sieve catalytic of binderless ZSM-11
Conversion of ethylene higher in agent, stability may be significantly improvement.
Specific embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Comparative example 1
10 grams of ZSM11 molecular sieves are weighed, after adding in 6.25 gram of 40% (weight) Ludox mixing, extrusion molding, through 120
DEG C drying is exchanged 3 times after 550 DEG C of roasting 2h with the ammonium nitrate solution of 0.8mol/L at 80 DEG C, washed 2 times, 120 DEG C of dryings,
540 DEG C of roasting 3h, then 550 DEG C of processing 2h of water vapour, gained catalyst are denoted as Cat-A.
Comparative example 2
10 grams of ZSM11 molecular sieves are weighed, after adding in 2.5 grams of aluminium oxide mixing, extrusion molding is dried, 550 through 120 DEG C
It is exchanged 3 times, washed 2 times, 120 DEG C of dryings, 540 DEG C of roastings with the ammonium nitrate solution of 0.8mol/L at 80 DEG C after DEG C roasting 2h
3h, then 550 DEG C of processing 2h of water vapour, gained catalyst are denoted as Cat-B.
Embodiment 1
10 grams of ZSM11 molecular sieves are weighed, after adding in 6.25 gram of 40% (weight) Ludox mixing, extrusion molding, through 120
DEG C drying, obtain sample A.5 grams of tetrabutylammonium bromide, 10 grams of 1,6- hexamethylene diamines and 30 grams of distilled water are previously added in reaction kettle
Mixture, 10 grams of sample A are placed in reaction kettle after porous stainless steel net upper seal at 180 DEG C progress gas-solid phase processor
14 hours.
Product is washed with distilled water after taking out, and is dried, molten with the ammonium nitrate of 0.8mol/L at 80 DEG C after 550 DEG C of roasting 2h
Liquid exchanges 3 times, washes 2 times, 120 DEG C of dryings, 540 DEG C of roasting 3h, and then 550 DEG C of processing 2h of water vapour, gained catalyst are denoted as
Cat-C.The sum of XRD spectra characteristic diffraction peak intensity with Cat-A in comparative example 1 is defined as 100%, other sample (such as Cat-
C, Cat-D, Cat-E, Cat-F) with its ratio be worth to relative crystallinity.The relative crystallinity of Cat-C is 138%.
Embodiment 2
10 grams of ZSM11 molecular sieves are weighed, after adding in 12 gram of 40% (weight) Ludox mixing, extrusion molding, through 120 DEG C
Drying, obtains sample B；The mixture of 10 grams of 1,6- hexamethylene diamines and 20 grams of distilled water is previously added in reaction kettle, by 10 grams of sample B
It is placed in reaction kettle after porous stainless steel net upper seal and gas-solid phase processor is carried out at 180 DEG C 24 hours.
Product is washed with distilled water after taking out, and is dried, molten with the ammonium nitrate of 0.3mol/L at 80 DEG C after 550 DEG C of roasting 2h
Liquid exchanges 3 times, washes 2 times, 120 DEG C of dryings, 570 DEG C of roasting 4h, and then 625 DEG C of processing 3h of water vapour, gained catalyst are denoted as
Cat-D.XRD results show that the relative crystallinity of Cat-D is 145%.
Embodiment 3
10 grams of ZSM11 molecular sieves are weighed, after adding in 40 grams of dioxide-containing silicas as the waterglass mixing of 20% (weight),
Extrusion molding through 120 DEG C of drying, obtains sample C.The mixed of 4 grams of 1,6- hexamethylene diamines and 15 grams of distilled water is previously added in reaction kettle
Object is closed, it is small that 10 grams of sample C are placed in reaction kettle after porous stainless steel net upper seal the progress gas-solid phase processor 90 at 120 DEG C
When.
Product is washed with distilled water after taking out, and is dried, and uses the hydrochloric acid solution of 0.4mol/L after 550 DEG C of roasting 2h at 65 DEG C
It exchanges 2 times, washes 2 times, 140 DEG C of dryings, 550 DEG C of roasting 3h, then 400 DEG C of processing 5h of water vapour, gained catalyst are denoted as
Cat-E.XRD results show that the relative crystallinity of Cat-E is 142%.
Embodiment 4
15 grams of ZSM11 molecular sieves are weighed, 2.5 gram of 40% (weight) Ludox is added in and 5 grams of dioxide-containing silicas is
After the waterglass mixing of 20% (weight), extrusion molding through 120 DEG C of drying, obtains sample D.3 gram 1 is previously added in reaction kettle,
10 grams of sample D are placed in reaction kettle after porous stainless steel net upper seal by the mixture of 6- hexamethylene diamines and 20 grams of distilled water
Gas-solid phase processor is carried out at 160 DEG C 48 hours.
Product is washed with distilled water after taking out, and is dried, molten with the ammonium nitrate of 0.5mol/L at 70 DEG C after 550 DEG C of roasting 2h
Liquid exchanges 2 times, washes 2 times, 140 DEG C of dryings, 600 DEG C of roasting 4h, and then 600 DEG C of processing 2h of water vapour, gained catalyst are denoted as
Cat-F.XRD results show that the relative crystallinity of Cat-F is 140%.
Comparative example 1~2 and Examples 1 to 4 reaction evaluating
It is the fixation that 24mm continuously flows that catalyst obtained by comparative example 1~2 and Examples 1 to 4 is respectively placed in internal diameter
Catalyst performance evaluation is carried out in bed reactor, 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.Product after reaction is cooled down through cooler carries out gas-liquid point
From.Gas and product liquid are formed with Agilent 7890A chromatographic system analysis, and product liquid uses PONA capillary columns,
Hydrogen flame detector.
The composition of unstripped gas is as shown in table 1, aromatization condition and the results are shown in Table 2 and table 3.As can be seen from Table 2
In the condition and range of investigation, the conversion ratio of the upper ethylene of catalyst Cat-C~Cat-F of binder free is more than 99%, liquefaction
Gas yield~30%, gasoline liquid yield>67%, arenes selectivity in liquid>42%, and silicon oxide-containing and alumina binder
ZSM11 molecular sieve catalysts Cat-A and Cat-B on analog value be respectively~94% ,~29% ,~64% and~40%.
With the extension (table 3) in reaction time, the stability of Cat-C~Cat-F catalyst is substantially better than Cat-A and Cat-B.
The composition (v%) of 1 unstripped gas of table
| H2 | N2 | COx | CH4 | C2H4 | C2H6 | C3H6 | C3H8 | C4H10 | O2 | H2S(ppm) | H2O(ppm) |
| 9.03 | 14.51 | 1.35 | 35.86 | 23.49 | 12.23 | 0.61 | 1.20 | 0.53 | 0.64 | 3800 | 1800 |
The catalysis reaction evaluating result (reaction time 5h) of 2 various catalyst of table
The catalysis reaction evaluating result (reaction time 50h) of 3 various catalyst of table
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 be covered by the protection scope of the present invention.
Claims (8)
1. the preparation method of the ZSM11 molecular sieve catalysts of a kind of binder free, which is characterized in that the catalyst is used to be catalyzed
Ethylene aromatisation generation gasoline and liquefied gas, specific preparation process are as follows in dry gas：
(1) ZSM11 molecular sieve powders are mixed with amorphous silica binding agent, wherein titanium dioxide in silica binder
The weight percentage of silicon is 10~50%；After shaping and drying, in the aqueous solution containing alkyl diamine and/or halogenation organic amine or
In steam, hydrothermal treatment is converted into 1 molecular sieve of binderless ZSM-11, and wherein crystallization temperature is 100~200 DEG C, crystallization time
It is 10~100 hours；
(2) 1 molecular sieve of binderless ZSM-11 prepared is passed through into ion exchange, dry, roasting, steam treatment, obtained nothing
The ZSM11 molecular sieve catalysts of binding agent.
2. the preparation method of the ZSM11 molecular sieve catalysts according to binder free described in claim 1, it is characterised in that：It is used
Silica binder be selected from Ludox, waterglass or its mixture.
3. the preparation method of the ZSM11 molecular sieve catalysts according to binder free described in claims 1 or 2, it is characterised in that：Two
The weight percentage of silica binder is 20~40%.
4. the preparation method of the ZSM11 molecular sieve catalysts according to binder free described in claim 1, it is characterised in that：Halogenation
Organic amine is selected from tetrabutylammonium bromide, and alkyl diamine is selected from 1,6- hexamethylene diamines.
5. the preparation method of the ZSM11 molecular sieve catalysts according to binder free described in claim 1, it is characterised in that：Hydro-thermal
The crystallization temperature of processing is 140~180 DEG C.
6. the preparation method of the ZSM11 molecular sieve catalysts according to the binder free of claim 1 or 5, it is characterised in that：Water
The crystallization time of heat treatment is 24~72 hours.
7. the preparation method of the ZSM11 molecular sieve catalysts according to binder free described in claim 1, it is characterised in that：It is described
In step (2), a concentration of 0.2-0.8mol/L of hydrochloric acid used in ion exchange or ammonium nitrate solution；The temperature of exchange is 60-80
℃；Drying temperature is 120~150 DEG C；Calcination temperature is 500~650 DEG C, and roasting time is 3~7h；Steam treatment temperature is
350-650 DEG C, the steam treatment time is 2-6h.
8. the preparation method of the ZSM11 molecular sieve catalysts according to binder free described in claim 1, it is characterised in that：It is described
Catalysis drying gas 10-60%v containing ethylene, H2S 100-5000ppm, COx 1.0-5.0%v, oxygen 0.1-1.5%v, water 1000-
4000ppm。
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