CN108435235A - A kind of mesoporous Zn-ZSM-5 molecular sieves and low cost preparation method - Google Patents
A kind of mesoporous Zn-ZSM-5 molecular sieves and low cost preparation method Download PDFInfo
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- CN108435235A CN108435235A CN201810251975.XA CN201810251975A CN108435235A CN 108435235 A CN108435235 A CN 108435235A CN 201810251975 A CN201810251975 A CN 201810251975A CN 108435235 A CN108435235 A CN 108435235A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
Abstract
The present invention relates to a kind of mesoporous 5 molecular sieves of Zn ZSM and low cost preparation method, mesoporous pore size concentrates on 5 30 nm, and specific surface area is 300 600 m2/g；Zinc oxide content is 0.1 ~ 10 wt% of molecular sieve total weight.The acid strength of mesoporous 5 molecular sieves of Zn ZSM is low, and the good dispersion of Zn, anti-carbon performance is strong, the fields such as mesoporous 5 molecular sieves of Zn ZSM can be used for being hydrocracked, catalytic cracking, hydrocarbon isomerization.
Description
Technical field
The present invention relates to Zeolite synthesis field, more particularly to a kind of mesoporous Zn-ZSM-5 molecular sieves and inexpensive preparation side
Method.
Background technology
ZSM-5 molecular sieve with properties such as special pore passage structure, excellent shape selectivity and hydrothermal stabilities due to urging
The fields such as change, adsorbing separation, ion exchange and green chemical industry play irreplaceable role.But due to ZSM-5 molecular sieve
Acidity it is stronger, be also easy to produce the side reactions such as cracking reaction, limit its application in such as isomerization, aromatization.Study table
It is bright, it, can also be right by the metal-modified processing of ZSM-5 molecular sieve progress, can not only reduce the acidity of ZSM-5 molecular sieve
ZSM-5 molecular sieve pore structure is modified.Hetero-atom molecular-sieve has uniqueness because introducing hetero atom in framework of molecular sieve
Catalytic performance, be widely used as the catalyst of petrochemical industry and organic chemical industry's production process.In recent years, Zn modified ZSM-5s point
Son sieve catalyst obtained, application is widely available due to its excellent catalytic performance.
CN200410066439.0 discloses a kind of method for the ZSM-5 molecular sieve containing hetero atom preparing nano-scale, adopts
With addition alkali metal salt, according to a certain percentage with charging sequence by additive, template, aluminium at 60~120 DEG C of crystallization temperature
It is mixed with hetero atom source alternative one (hetero atom includes Ga, V, Fe, Zn, Ni, Co and Cr) and silicon source, under the conditions of static or agitation
Crystallization 1~15 day.The crystallite dimension of molecular sieve is between 40~200nm, and specific surface area is between 300~600m2/g.The present invention overcomes
The previous limitation for preparing nano-sized molecular sieve and being only limited to the ZSM-5 molecular sieve containing aluminium.It is an advantage of the invention that synthesis condition can
It is selected between static or agitation state；Nontoxic operation；Crystallite dimension is controllable and skeleton contains hetero atom, and metallic atom type is more；It is brilliant
It is low to change temperature；It is easy to operate.
CN201510031312.3 disclose a kind of Template-free method little crystal grain Zn-ZSM-5 catalyst preparation method and its
Using being related to the preparation of small crystal grain molecular sieve.Silicon source is mixed with aqueous slkali, obtains mixed liquor；Silicon source is added in mixed liquor, then
Zinc salt is added, after aging, hydro-thermal process filters, and washs, dry, and Zn-ZSM-5 molecular sieve catalysts are obtained after roasting；Grain size
Zn-ZSM-5 molecular sieve catalysts are carried out ion exchange by 200-300nm in ammonium salt solution, be then filtered, washed, dry,
To get to Template-free method little crystal grain Zn-ZSM-5 catalyst, the Template-free method little crystal grain Zn-ZSM-5 catalyst can be for roasting
It is prepared in gasoline and is applied using methanol.Without adding template in catalyst preparation process, obtained Zn-ZSM-5 is that grain size is equal
One, the small crystal grain molecular sieve of regular appearance, and a step obtains Zn-ZSM-5 catalyst, reduces the step of conventional method load Zn
Suddenly.
CN201510946456.1 discloses a kind of preparation method of preparing gasoline by methanol catalyst nano Zn-ZSM-5, is related to
Methanol derivatives.1) prepare silicon source, template and aqueous slkali mixed liquor；2) silicon source, zinc salt are added into mixed liquor, stirring is equal
Reflux after even, obtained turbid solution centrifuge, are dry, roasting, and obtain nanometer Zn-ZSM-5 molecular sieve；3) step 2) is obtained
Nanometer Zn-ZSM-5 molecular sieve is roasted through ion exchange, centrifugation, drying to get preparing gasoline by methanol catalyst nano Zn-
ZSM-5, the preparing gasoline by methanol catalyst nano Zn-ZSM-5 can be applied in preparing gasoline by methanol.Preparing gasoline by methanol catalyst is received
Rice Zn-ZSM-5 shows good performance in preparing gasoline by methanol reaction.
Above with respect to nanometer or little crystal grain Zn-ZSM-5 molecular sieves, there are a common problems：The crystal grain of molecular sieve is nanometer
Grade detaches difficulty from mother liquor, generally selects centrifugation after synthesis, this has low separation efficiency, operation in the industrial production
Problem of high cost.
Invention content
To solve the above problems, a kind of mesoporous Zn-ZSM-5 molecular sieves of present invention offer and preparation method, are based on the screening
The catalyst and preparation method of son sieve, the mesoporous Zn-ZSM-5 molecular sieves can be used for being hydrocracked, catalytic cracking, hydro carbons are different
The fields such as structure.
A kind of mesoporous Zn-ZSM-5 molecular sieves, mesoporous pore size concentrate on 5-30nm, specific surface area 300-600m2/g；Oxygen
Change 0.1~10% that Zn content is molecular sieve total weight.
Molecular sieve is further improved, a kind of mesoporous Zn-ZSM-5 molecular sieves, mesoporous pore size concentrates on 5-30nm, specific surface
Product is 300-600m2/g；Zinc oxide content is the 0.1~10% of molecular sieve total weight, and molecular sieve surface Zn content compares molecular sieve
Internal Zn content is high, preferably 0.2~2 times high.
The present invention also provides a kind of preparation methods of mesoporous Zn-ZSM-5 molecular sieves, include the following steps：
(1) at a certain temperature, by deionized water, silicon source, zinc source, acid source, template (SDA) and silicon source in stirring condition
Lower be uniformly mixed is prepared into gel, and adjusting molar ratio of material is (0.005~0.05) Al2O3:(0.05~0.25) Na2O:
1SiO2:(20~60) H2O:(0.01~0.2) SDA:(0.001~0.1) ZnO；
(2) it will be transferred in the stainless steel cauldron containing polytetrafluoroethyllining lining after the gel aging obtained in step (1)
Crystallization is sealed, after waiting for crystallization, by crystallization product cooling, is filtered to remove mother liquor, filter cake is washed with deionized to neutrality, does
It is dry to obtain Zn-ZSM-5 molecular sieves；
(3) by the Zn-ZSM-5 molecular sieves obtained in step (2) through a series of processing such as exchange, filtering, drying, roasting,
Obtain H-type Zn-ZSM-5 molecular sieves.
The present invention is further improved mesoporous Zn-ZSM-5 molecular sieves, after obtaining H-type Zn-ZSM-5 molecular sieves, passes through dipping
Method impregnates zinc compound on the surface of H-type Zn-ZSM-5 molecular sieves and is modified again so that molecular sieve surface Zn content score
The internal Zn content of son sieve is high, preferably incipient impregnation, obtains the improvement H-type Zn-ZSM-5 molecular sieves of Zn modifications, that is, improves Zn-
ZSM-5 molecular sieve.Wherein, the zinc compound is one or more of zinc nitrate, zinc acetate, zinc chloride and zinc sulfate,
It is preferred that zinc nitrate.
Silicon source described in step (1) be commercial water glass, Ludox, ethyl orthosilicate, one kind in solid silicone or
It is several；Source of aluminium is one or more of sodium metaaluminate, aluminium isopropoxide, aluminum sulfate.
SDA described in step (1) is one or more of trimethylamine (TMA), methyl ethylamine, pyrroles, beautiful jade, can also be
In common tetrapropylammonium hydroxide (TPAOH), 4-propyl bromide (TPABr), 1,6- hexamethylene diamines, n-butylamine, hexylene glycol
One or more of one or more, preferably trimethylamine (TMA), methyl ethylamine, pyrroles, beautiful jade.
Acid source described in step (1) is the mixture of one or more of sulfuric acid, hydrochloric acid, nitric acid, oxalic acid, acetic acid,
One or more of preferably sulfuric acid, hydrochloric acid and nitric acid, a concentration of 0.1~8mol/L of acid solution.
Zinc source in step (1) and (3) is one or more of zinc nitrate, zinc acetate, zinc chloride and zinc sulfate.
Silicon source described in step (1) can also be one or both of diatomite, opal, and silicon source can also be height
One or more of ridge soil, rectorite, perlite, montmorillonite, zinc source can also be one kind or two in smithsonite, zincite
Kind.
Aging temperature described in step (2) is 25~80 DEG C, preferably 35~70 DEG C；Ageing time be 2~16h, preferably 3
~10h.
Crystallization temperature described in step (2) is 100~200 DEG C, preferably 120~180 DEG C；Divide 1~5 section of temperature programming,
It is preferred that 1~3 section；Preferably be segmented not isothermal heating, non-isothermal temperature-gradient method processing, heating rate first quick and back slow, 100 DEG C with
The preceding heating rate with 6~8 DEG C/min heats up, and 20~30 DEG C are a warming-up section, and temperature section processing time is 0.5~5 small
When；It is heated up with the heating rate of 3~5 DEG C/min between 100~200 DEG C, 10~20 DEG C are a warming-up section, temperature section processing
Time is 0.5~8 hour.The present invention is handled using non-isothermal temperature-gradient method, is conducive to Zn-ZSM-5 Crystallization of Zeolite processes
Nucleation rate and growth rate control, can control mesoporous size and quantity, and then can improve the activity and mesh of catalyst
Selectivity of product.Crystallization time is 12~120h, preferably 24~96h.
400~800 DEG C of calcination temperature described in step (3), preferably 400~600 DEG C；2~10h of roasting time；It exchanges
Reagent is one kind in hydrochloric acid, nitric acid, sulfuric acid, ammonium chloride or ammonium nitrate；
The surface modification of molecular sieve described in step (3) uses incipient impregnation zinc compound, the wherein quality of ZnO
Score is 0.5~15%, preferably 0.5~10%.
The present invention also provides a kind of isomerization catalyst and preparation method, the isomerization catalyst is by weight percentage
Including 35~90%H type Zn-ZSM-5 molecular sieves or Zn-ZSM-5 molecular sieves are improved, preferably 45~85%；5~60% hydrogen-oxygens
Change aluminium dry glue binder, preferably 10~50%；0.5~15% metal active constituent of dipping, preferably 0.5~10%；It is described
Metal active constituent be one or more of Fe, Co, Ni and Mo, carrying method is infusion process, preferably incipient impregnation.
The preparation method of isomerization catalyst of the present invention is as follows：Obtained H-type Zn-ZSM-5 molecular sieves or improvement Zn-ZSM-
5 molecular sieves and aluminum hydroxide solid elastomer mixed-forming, then impregnate base metal active component and roast and obtain isomerization catalyst.
By the present invention isomerization catalyst be used for normal octane hydroisomerization reaction, 200~400 DEG C, 1~
4MPa, WHSV=1~10h-1Under the conditions of hydrogen to oil volume ratio 100~500, normal octane conversion ratio is above 85%, isomery octane
Selectivity is even more that 87.37% is up at 220 DEG C.
Compared with prior art, the present invention has the following advantages：
1, the present invention by Zn-ZSM-5 molecular sieve of the one-step synthesis method skeleton containing Zn, synthetic method is simple, due to Zn into
Entering framework of molecular sieve causes crystal structure to change, and generation is mesoporous, while improving the dispersibility of Zn, this will make reactant
Diffusional resistance reduces, and improves anti-carbon performance.
2, Zn-ZSM-5 molecular sieve surfaces Zn content of the present invention is higher than Zn content inside molecular sieve, surface Zn atoms and Al hydroxyls
Base interaction causes strong acid remitted its fury to middle strong acid, so that the acid strength of molecular sieve is reduced, reduces hydro carbons from the root cause and split
The side reactions such as change occur, and improve the selectivity of isohydrocarbon.
3, by the mesoporous Zn-ZSM-5 molecular sieves obtained by the present invention for be hydrocracked, catalytic cracking, hydrocarbon isomerization
Equal fields, load base metal are greatly slowed down as hydrogenation-dehydrogenation metal active centres component in catalyst metals activity
The heart is poisoned because of caused by the miscellaneous elements such as the S that contains in raw material, is improved the stability of catalyst, is extended the longevity of catalyst
Life.It is used as active component especially with one or more of Fe, Co, Ni and Mo, it can be simultaneously for hydrocarbon isomerization reaction
Improve the activity and selectivity of catalyst.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram for the Zn-ZSM-5 molecular sieves that the embodiment of the present invention 1 is prepared.
Fig. 2 is the N for the Zn-ZSM-5 molecular sieves that the embodiment of the present invention 1 is prepared2Adsorption-desorption isothermal.
Fig. 3 is the graph of pore diameter distribution for the Zn-ZSM-5 molecular sieves that the embodiment of the present invention 1 is prepared.
Fig. 4 is the Zn-ZSM-5 molecular sieves (synthetic sample) and business ZSM-5 molecules that 1-1 of the embodiment of the present invention is prepared
Sieve the NH of (commercial sample)3Temperature programmed desorption (NH3- TPD) spectrogram.
Specific implementation mode
Below by way of the advantageous effect of the specific embodiment implementation process that the present invention will be described in detail and generation, it is intended to contribute to
More fully understand the present invention essence and feature, not as to this case can practical range restriction.Quotient used in embodiment
Industry sample is SiO2/Al2O3The ZSM-5 molecular sieve that molar ratio is 50.
In order to reflect isomerization ability of the catalyst to normal octane, following evaluation index is defined：The conversion ratio of normal octane
X, the calculating of the selective S of isooctane is provided by formula (1) and (2).
In formula：
[A]Raw materialFor normal octane peak area proportion, % in raw material；
[A]ProductFor normal octane peak area proportion, % in product；
[B]ProductFor the sum of all isooctane peak areas proportion, % in product.
Embodiment 1
The present embodiment provides a kind of Ni-Mo/Zn-ZSM-5 catalyst, and preparation method includes the following steps：
1, mesoporous Zn-ZSM-5 molecular sieves are prepared
(1) 7.4g NaAlO are weighed2With 170g Zn (NO3)2·6H2O is dissolved in 6100g deionized waters, is then added dropwise
60g TMA are added after stirring 5min in 200g sulfuric acid (4mol/L), and 1420g waterglass is added (containing 27.6wt%'s after stirring 1h
SiO2, the Na of 7.1wt%2The H of O and 65.3wt%2O), 4h is mixed at 30 DEG C, a mole group for mixture becomes
0.005Al2O3:0.25Na2O:1SiO2:60H2O:0.15SDA:0.09ZnO。
(2) mixture that step (1) obtains is warming up to 70 DEG C of aging 4h, then poured this solution into band polytetrafluoroethylene (PTFE)
In the stainless steel crystallizing kettle of lining, it is warming up to 130 DEG C of crystallization for 24 hours, then heats to 170 DEG C of static crystallization 48h.After crystallization,
Cooling is filtered to remove mother liquor, and washing to neutrality is dry at 120 DEG C, obtains crystallization product Zn-ZSM-5 molecular sieves.It is composed by XRD
Figure (Fig. 1) can prove that the sample of synthesis is the Zn-ZSM-5 molecular sieves of high-purity, by N2Adsorption/desorption isotherms (Fig. 2) and hole
Diameter distribution map (Fig. 3) proves that there is the Zn-ZSM-5 molecular sieves of synthesis meso-hole structure, mesoporous pore size to concentrate on 5~30nm, compare table
Area is 580m2/g.The Zn-ZSM-5 molecular sieves N of the present invention2There are adsorption-desorption isothermal double hysteresis loops to be distributed, acid strength
It is low, and the anti-poisoning capability of catalyst prepared is strong.
(3) it is 1 according to solid-to-liquid ratio by Zn-ZSM-5 molecular sieves:10 are added in the ammonium chloride solution of a concentration of 1mol/L,
4h is mixed at 60 DEG C, filters, drying in kind exchanges once again, is put into Muffle furnace the high temperature at 550 DEG C and roasts
It burns 6h and obtains H-type Zn-ZSM-5 molecular sieves；Then the ZnO that impregnating effect score is 5% again.By NH3- TPD spectrograms (Fig. 4) prove
The strong acid desorption temperature of the Zn-ZSM-5 molecular sieves of synthesis is 350 DEG C, and the strong acid desorption temperature of commercial sample is 450 DEG C, table
The Zn-ZSM-5 molecular sieves of bright synthesis have significant lower acid strength.
2, Ni-Mo/Zn-ZSM-5 catalyst is prepared
By the above-mentioned Zn-ZSM-5 molecular sieves handled well of 30g, mixed with 15g aluminum hydroxide solid elastomers and 20g deionized waters
Even, then extruded moulding, the dry 4h at 120 DEG C, 550 DEG C of roasting 5h obtain molecular sieve carrier, then use incipient impregnation
Method impregnates the MoO of the NiO and 5.0wt% of 5.0wt%3, Ni-Mo/Zn-ZSM-5 catalyst is made.
Embodiment 2
The present embodiment provides a kind of Co-Mo/Zn-ZSM-5 catalyst, preparation process is joined with embodiment 1, only modulation part
Number, it is specific as follows：
(1) it is silicon source using solid silicone as silicon source, aluminum sulfate, zinc nitrate is zinc source, hydrochloric acid (2mol/L) is acid source, pyrroles
With the mixture (molar ratio 1 of morpholine:1) it is SDA, adjusting inventory makes the molar ratio of its Zeolite synthesis system be
0.02Al2O3:0.05Na2O:1SiO2:20H2O:0.05SDA:0.002ZnO。
(2) aging condition：50 DEG C, 8h；Crystallization condition：120 DEG C of crystallization 12h, for 24 hours, 180 DEG C of crystallization are for 24 hours for 150 DEG C of crystallization.
(3) hydrochloric acid solution that solution is 0.5mol/L used in exchanging, calcination temperature are 450 DEG C, roasting time 8h,
The mass fraction of oxide impregnation zinc is 12wt%.
(4) active metal load capacity is the MoO of the CoO and 6wt% of 2wt%3。
Embodiment 3
The present embodiment provides a kind of Ni-Mo/Zn-ZSM-5 catalyst, preparation process is joined with embodiment 1, only modulation part
Number, it is specific as follows：
(1) it is silicon source using solid silicone as silicon source, aluminum sulfate, zinc chloride is zinc source, acetic acid (6mol/L) is acid source, first and second
Amine is SDA, and adjusting inventory makes the molar ratio of its Zeolite synthesis system be 0.03Al2O3:0.15Na2O:1SiO2:40H2O:
0.10SDA:0.05ZnO。
(2) aging condition：40 DEG C, 12h；Crystallization condition：It is segmented not isothermal heating, first with the heating of 7 DEG C/min speed
Rate heats up, and 20 DEG C are a warming-up section, and temperature section processing time is 0.5 hour；With the heating of 4 DEG C/min speed after 100 DEG C
Rate heats up, and 10 DEG C are a warming-up section, and temperature section processing time is 0.5 hour；Non-isothermal temperature-gradient method handles Zn-ZSM-5
The nucleation rate and growth rate of Crystallization of Zeolite process are controllable, can control mesoporous size and quantity is (mesoporous to be distributed more
It is uniform, it is concentrated mainly on 5-10nm, and 20%) mesoporous quantity increases, and then the activity and purpose product of catalyst can be improved
Selectivity.
(3) sulfuric acid solution that solution is 0.5mol/L used in exchanging, calcination temperature are 520 DEG C, roasting time 4h,
The mass fraction of oxide impregnation zinc is 6wt%.
(4) active metal load capacity is the MoO of the NiO and 3wt% of 5wt%3。
Embodiment 4
The present embodiment provides a kind of Ni-Mo/Zn-ZSM-5 catalyst, and preparation process is joined with embodiment 1, only modulation part
Number, it is specific as follows：
(1) it is silicon source using solid silicone as silicon source, aluminum sulfate, zinc chloride is zinc source, sulfuric acid (5mol/L) is acid source, morpholine
For SDA, adjusting inventory makes the molar ratio of its Zeolite synthesis system be 0.01Al2O3:0.10Na2O:1SiO2:30H2O:
0.20SDA:0.08ZnO。
(2) aging condition：60 DEG C, 10h；Crystallization condition：It is segmented not isothermal heating, first with the heating of 8 DEG C/min speed
Rate heats up, and 20 DEG C are a warming-up section, and temperature section processing time is 0.5 hour；The heating rate of 3 DEG C/min after 100 DEG C
Heating, 10 DEG C are a warming-up section, and temperature section processing time is 0.5 hour；Non-isothermal temperature-gradient method handles Zn-ZSM-5 points
The nucleation rate and growth rate of son sieve crystallization process are controllable, and can controlling mesoporous size and quantity, (mesoporous distribution is more equal
One, it is concentrated mainly on 8-15nm, and 25%) mesoporous quantity increases, and then activity and the purpose product choosing of catalyst can be improved
Selecting property.
(3) ammonium nitrate solution that solution is 0.5mol/L used in exchanging, calcination temperature are 580 DEG C, and roasting time is
2h。
(4) active metal load capacity is the MoO of the NiO and 3wt% of 5wt%3。
Embodiment 5
The present embodiment provides a kind of Ni-Mo/Zn-ZSM-5 catalyst, preparation process is joined with embodiment 3, only modulation part
Number, it is specific as follows：
(1) be silicon source using the opal after activation as the rectorite after silicon source, activation, the smithsonite after activation be zinc source,
Acetic acid (6mol/L) is acid source, methyl ethylamine SDA, and adjusting inventory makes the molar ratio of its Zeolite synthesis system be
0.03Al2O3:0.15Na2O:1SiO2:40H2O:0.10SDA:0.05ZnO.The activation of wherein opal is by opal 600
Roast 4h under conditions of DEG C, the activation of rectorite is by rectorite mineral and NaOH according to mass ratio 1:It is added after 1.5 mixing few
Water extruded moulding, 160 DEG C of drying are measured, the activation of smithsonite is that smithsonite is roasted 4h under conditions of 800 DEG C.
Embodiment 6
The present embodiment includes the following steps by catalyst for fixed bed reaction test activity：
Reaction tube of the 5g Catalyst packings that above-described embodiment 1 is prepared on micro fixed-bed reactor device
In, it starts to warm up at room temperature, heating rate is 2 DEG C/min, and temperature is increased to 140 DEG C and starts to vulcanize, and temperature is increased to 320 DEG C simultaneously
It keeps 2h after cure to terminate, reacts 2h after being naturally cooling to 220 DEG C, collect reaction product and analyzed.It protects in the whole process
It is 9g/h, system pressure 1.5MPa, hydrogen to oil volume ratio 300 to hold normal octane feed rate.Catalysis reaction result is shown in Table 1.
Embodiment 7
The present embodiment, by catalyst for fixed bed reaction test activity, step exists with embodiment 6, parameter difference
In：Catalyst is the catalyst that embodiment 2 obtains, and reaction temperature is 240 DEG C.
Embodiment 8
The present embodiment, by catalyst for fixed bed reaction test activity, step exists with embodiment 6, parameter difference
In：Catalyst is the catalyst that embodiment 3 obtains, and reaction temperature is 260 DEG C.
Embodiment 9
The present embodiment, by catalyst for fixed bed reaction test activity, step exists with embodiment 6, parameter difference
In：Catalyst is the catalyst that embodiment 4 obtains, and reaction temperature is 280 DEG C.
Embodiment 10
The present embodiment, by catalyst for fixed bed reaction test activity, step exists with embodiment 6, parameter difference
In：Catalyst is the catalyst that embodiment 5 obtains, and reaction temperature is 260 DEG C.
Comparative example 1
In order to prove the technique effect of technical solution of the present invention, the present invention is also provided with comparative example, in this comparative example
The molecular sieve used for business micropore ZSM-5 molecular sieve, molding, dipping and etc. with embodiment 1.
Comparative example 2
The present embodiment, by catalyst for fixed bed reaction test activity, step exists with embodiment 6, parameter difference
In：Catalyst is the catalyst that comparative example 1 obtains, and reaction temperature is 280 DEG C.
Comparative example 3
This comparative example carrier is prepared with embodiment 4, is a difference in that crystallization process is segmentation isothermal heating, 140 DEG C of crystallization
12h, 170 DEG C of crystallization are for 24 hours.The preparation of catalyst and composition are with embodiment 4, and evaluation condition is the same as embodiment 9.
The measurement result of the isomerization product of 1 each embodiment and comparative example of table
| Conversion ratio (%) | Isomer selective (%) | Cracking rate (%) | Coking yield (%) | |
| Embodiment 6 | 87.86 | 87.37 | 12.21 | 0.2 |
| Embodiment 7 | 92.27 | 86.07 | 12.06 | 0.25 |
| Embodiment 8 | 98.12 | 89.03 | 10.61 | 0.3 |
| Embodiment 9 | 98.31 | 78.07 | 17.16 | 0.25 |
| Embodiment 10 | 98.23 | 89.05 | 10.51 | 0.28 |
| Comparative example 2 | 99.30 | 2.10 | 97.92 | 1.1 |
| Comparative example 3 | 97.43 | 65.14 | 32.23 | 0.41 |
As it can be seen from table 1 mesoporous Zn-ZSM-5 catalyst provided by the invention has excellent isomerization reaction activity,
There is higher isoparaffin selectivity and lower cracking rate (i.e. high liquid yield) and coking yield compared with comparative example.
Under conditions of described in embodiment 8, stability experiment is carried out to catalyst, the results showed that after reacting 800h, catalyst turns
Rate and isomer selective are kept at 98.05,88.95% or more, cracking rate and coking yield be respectively lower than 10.70,
0.3%.Therefore, mesoporous Zn-ZSM-5 catalyst provided by the invention has more excellent isomerization ability and activity stabilized
Property.In addition, the mesoporous Zn-ZSM-5 molecular sieves one-step method of the present invention is made, it is simple for process, and using base metal as metal
Active component, it is cheap, have good economic benefit and prospects for commercial application.
Claims (10)
1. a kind of mesoporous Zn-ZSM-5 molecular sieves, it is characterised in that：Mesoporous pore size concentrates on 5-30 nm, specific surface area 300-
600 m2/ g, zinc oxide content is the 0.1 ~ 10% of molecular sieve total weight in molecular sieve.
2. a kind of mesoporous Zn-ZSM-5 molecular sieves, it is characterised in that：Mesoporous pore size concentrates on 5-30 nm, specific surface area 300-
600 m2/ g, zinc oxide content is the 0.1 ~ 10% of molecular sieve total weight in molecular sieve, and molecular sieve surface Zn content is than in molecular sieve
Portion's Zn content is high.
3. a kind of mesoporous Zn-ZSM-5 molecular sieves according to claim 2, it is characterised in that：The molecular sieve surface zinc contains
Amount is 0.2 ~ 2 times higher than Zn content inside molecular sieve.
4. a kind of preparation method of mesoporous Zn-ZSM-5 molecular sieves as described in claim 1, it is characterised in that：It includes as follows
Step：(1) at a certain temperature, deionized water, silicon source, zinc source, acid source, template and silicon source are mixed under agitation
Even to be prepared into gel, adjusting molar ratio of material is (0.005 ~ 0.05) Al2O3: (0.05~0.25)Na2O: 1SiO2: (20~
60)H2O: (0.01~0.2)SDA: (0.001~0.1)ZnO；
(2) it will be transferred in the stainless steel cauldron containing polytetrafluoroethyllining lining and seal after the gel aging obtained in step (1)
Crystallization after waiting for crystallization, by crystallization product cooling, is filtered to remove mother liquor, and filter cake is washed with deionized to neutrality, dry
To Zn-ZSM-5 molecular sieves.
5. a kind of preparation method of mesoporous Zn-ZSM-5 molecular sieves as claimed in claim 2, it is characterised in that：It includes as follows
Step：(1) deionized water, silicon source, zinc source, acid source, template and silicon source are mixed under agitation at a certain temperature
Even to be prepared into gel, adjusting molar ratio of material is (0.005 ~ 0.05) Al2O3: (0.05~0.25)Na2O: 1SiO2: (20~
60)H2O: (0.01~0.2)SDA: (0.001~0.1)ZnO；
(2) it will be transferred in the reaction kettle containing polytetrafluoroethyllining lining after the gel aging obtained in step (1) and seal crystallization, waited for
After crystallization, by crystallization product cooling, it is filtered to remove mother liquor, filter cake is washed with deionized to neutrality, is dried to obtain Zn-
ZSM-5 molecular sieve；
(3) it impregnates zinc compound again on the surface of Zn-ZSM-5 molecular sieves to be modified so that molecular sieve surface Zn content ratio
Zn content is high inside molecular sieve.
6. a kind of preparation method of mesoporous Zn-ZSM-5 molecular sieves according to claim 5, it is characterised in that：Step (3),
The surface modification of the Zn-ZSM-5 molecular sieves uses incipient impregnation zinc compound.
7. a kind of preparation method of mesoporous Zn-ZSM-5 molecular sieves according to claim 4 or 5, it is characterised in that：It is described
Crystallization steps are segmented not isothermal heating treatment, and first quick and back slow, 100 DEG C in the past with the heating of 6 ~ 8 DEG C/min for heating rate
Rate heats up, and 20 ~ 30 DEG C are a warming-up section, and temperature section processing time is 0.5 ~ 5 hour；With 3 ~ 5 between 100 ~ 200 DEG CoThe heating rate of C/min heats up, and 10 ~ 20 DEG C are a warming-up section, and temperature section processing time is 0.5 ~ 8 hour.
8. a kind of preparation method of mesoporous Zn-ZSM-5 molecular sieves according to claim 4 or 5, it is characterised in that：It is described
Crystallization temperature be 100 ~ 200 DEG C, point 1 ~ 5 section of temperature programming.
9. a kind of preparation method of mesoporous Zn-ZSM-5 molecular sieves according to claim 4 or 5, it is characterised in that：Step
(1) in, the template is one or more of trimethylamine TMA, methyl ethylamine, pyrroles, beautiful jade or the template is four
One or more of propyl ammonium hydroxide, 4-propyl bromide, 1,6- hexamethylene diamines, n-butylamine, hexylene glycol.
10. a kind of preparation method of mesoporous Zn-ZSM-5 molecular sieves according to claim 4 or 5, it is characterised in that：Step
(1) zinc compound described in zinc source, step (3) described in is one kind in zinc nitrate, zinc acetate, zinc chloride and zinc sulfate
Or it is several；Or the zinc source described in step (1), the zinc compound described in step (3) are one kind in smithsonite, zincite
Or two kinds；
Acid source described in step (1) is the mixture of one or more of sulfuric acid, hydrochloric acid, nitric acid, oxalic acid, acetic acid；
Silicon source described in step (1) is one or more of waterglass, Ludox, ethyl orthosilicate, solid silicone；Or
Person, the silicon source described in step (1) are one or both of diatomite, opal；
Silicon source described in step (1) is one or more of sodium metaaluminate, aluminium isopropoxide, aluminum sulfate；Alternatively, step (1)
Described in silicon source be kaolin, rectorite, perlite, one or more of montmorillonite.
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