CN108452840A - A kind of isomerization catalyst and preparation method - Google Patents
A kind of isomerization catalyst and preparation method Download PDFInfo
- Publication number
- CN108452840A CN108452840A CN201810251965.6A CN201810251965A CN108452840A CN 108452840 A CN108452840 A CN 108452840A CN 201810251965 A CN201810251965 A CN 201810251965A CN 108452840 A CN108452840 A CN 108452840A
- Authority
- CN
- China
- Prior art keywords
- zsm
- mesoporous
- isomerization catalyst
- zinc
- molecular sieves
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J29/048—Zincosilicates, Aluminozincosilicates
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- 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
-
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The present invention relates to a kind of isomerization catalyst and preparation methods, the isomerization catalyst includes mesoporous 5 molecular sieves of Zn ZSM of 30 ~ 85%H types or improved mesoporous 5 molecular sieves of Zn ZSM by weight percentage, 8 ~ 56% aluminium oxide, magnalium hydrotalcite and/or Kaolin binder, preferably 12 ~ 48%；Impregnate 0.2 ~ 14% metal active constituent.The metal active constituent is one or more of Fe, Co, Ni, Mo and W.The activity and selectivity of catalyst is high, and anti-carbon performance is good.
Description
Technical field
The present invention relates to PETROLEUM PROCESSING catalyst fields, more particularly to using mesoporous Zn-ZSM-5 molecular sieves as the isomery of carrier
Change catalyst and preparation method.
Background technology
Gasoline is one of the main fuel of current car engine, plays the effect that do not replace.But with environmental protection
Dynamics is increasingly enhanced, and gasoline standard is also gradually increased.The content of reduction sulphur and alkene is the main task of clean gasoline production,
Wherein alkene is antiknock component, and the reduction of content certainly will cause the loss of octane number.It can by adding ether compound
To improve the octane number of gasoline, but the ethers added can pollute underground water.Although alkylation techniques can also improve
The octane number of gasoline, but the technology used catalyst is mostly the strong acid for polluting environment and etching apparatus.Catalytic reforming process also because
For China is mostly catalytically cracked gasoline and is limited.Oil plant is more likely to improve gasoline octane by isomerization technique at this stage
Value can increase substantially its octane number by being band branched paraffin by straight chain alkane isomerization.But used in current isomerization technique
Catalyst is mostly noble metal catalyst, it is of high cost and also need to raw material carry out multistep pretreatment.Therefore, it develops cheap
High stability isomerization catalyst is to improve one of very effective means of gasoline quality.
Most of hydrocarbon isomerization technology is using the bifunctional catalyst of carrier containing solid acid and noble metal, i.e. solid acid
Property carrier material provides isomery function, metal active constituent provides dehydrogenation-hydrogenating function.Metal active site makes dehydrogenation of hydrocarbons produce
Raw carbonium ion forms intermediate active transition state, and it is different that the branched alkene of skeletal isomerization reaction generation is then carried out on acid site
Structure product is finally hydrogenated to band branched paraffin in metal active position.Due to hydrocarbon cracking in reaction process, cyclisation and oligomeric
The presence of equal side reactions generates the lower by-product of octane number, constitutes the main source of isomerization process loss of octane number.Cause
This, the main target of isomerization technique is to find to have high activity and highly selective catalyst, to inhibit the hair of side reaction
It is raw.
CN106732752A discloses a kind of preparation method of C5, C6 alkane isomerization catalyst, using modenite with
Inorganic binder is molded, after being impregnated with hydrophobicity organic amine -ol solution, then the group VIIIs metal such as Supported Pt Nanoparticles, ruthenium, rhodium and palladium,
So that noble metal is reached nano-dispersion degree on carrier, improve catalyst activity, reduces noble-metal-supported amount, it is cost-effective.
CN106799257A discloses a kind of alkane isomerization catalyst and preparation method thereof, by phosphor-silicon-aluminum molecular sieve and
VIII group noble metal forms, which shows more excellent performance in isomerization reaction.
CN106140189A discloses a kind of preparation method of Performance of Isomerization Catalysts for Light n-Paraffin and the isomery of light paraffins
Change method, by coprecipitation and hydro-thermal process method synthesis of solid super acidic catalyst, then carried noble metal Pt, is used for positive penta
Alkane isomerization, the catalyst and reaction process have the characteristics that free from environmental pollution, etching apparatus, activity and selectivity be not high.
CN106635137A discloses a kind of low-carbon alkanes isomerization method, low-carbon alkanes are carried out dehydrating successively and
Then rectification process contacts with aluminium containing oxychloride and carries out hydroisomerization reaction, can effectively improve Al catalysts containing oxychloride
Isomerization activity, improve product octane number.
Although foregoing invention improves the activity of isomerization catalyst, but its selectivity is not yet received and is obviously improved, together
When there is no fundamentally solve the problems, such as that noble metal is expensive.Therefore the present invention is using low cost, high activity and high selection
Property mesoporous Zn-ZSM-5 molecular sieves or improved mesoporous Zn-ZSM-5 molecular sieves be acid carrier, while using Fe, Co, Ni,
The base metals such as Mo and W prepare hydrocarbon isomerization catalyst as hydrogenation-dehydrogenation activated centre, have wide commercial Application
Foreground.
Invention content
To solve the above problems, a kind of isomerization catalyst of present invention offer and preparation method, catalyst is with mesoporous Zn-
ZSM-5 molecular sieve or improved mesoporous Zn-ZSM-5 molecular sieves are carrier, load Fe, Co, Ni, Mo and W isoreactivity component.
A kind of isomerization catalyst, by weight percentage, including 30~85%H types are mesoporous for the isomerization catalyst
Zn-ZSM-5 molecular sieves or improved mesoporous Zn-ZSM-5 molecular sieves, preferably 42~78%；8~56% aluminium oxide, magnalium water
Talcum and/or knot agent, preferably 12~48%；0.2~14% metal active constituent of dipping, preferably 0.8~8%；Described
Metal active constituent is one or more of Fe, Co, Ni, Mo and W, and carrying method is infusion process, preferably multiple maceration.
The preparation method of isomerization catalyst of the present invention is as follows：By mesoporous H-type Zn-ZSM-5 molecular sieves or improved Zn-
ZSM-5 molecular sieve and aluminium oxide, magnalium hydrotalcite and/or Kaolin binder mixed-forming, then impregnate base metal activearm
Divide and roasts to obtain isomerization catalyst.
The mesoporous Zn-ZSM-5 molecular sieves of the H-type, mesoporous pore size concentrate on 4-35nm, specific surface area 350-680m2/
g；Zinc oxide content is the 0.2~9.5% of molecular sieve total weight.
The present invention also provides a kind of preparation methods of the mesoporous Zn-ZSM-5 molecular sieves of H-type, 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 (0.002~0.06) Al2O3:(0.04~0.25) Na2O:
1SiO2:(10~50) H2O:(0.02~0.25) SDA:(0.001~0.12) 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 zinc nitrate, zinc acetate, zinc chloride, one or more of zinc sulfate, excellent
Select zinc acetate.
Improved mesoporous Zn-ZSM-5 molecular sieves of the present invention, mesoporous pore size concentrate on 4-35nm, and specific surface area is
350-680m2/g；Zinc oxide content be molecular sieve total weight 0.2~9.5%, molecular sieve surface Zn content than molecular sieve inside
Zn content is high, preferably 0.2~2 times high.Silicon source described in step (1) is waterglass, Ludox, ethyl orthosilicate, solid silicon
One or more of glue；Source of aluminium is one or more of sodium metaaluminate, aluminium isopropoxide, aluminum sulfate；The zinc source is
One or more of zinc nitrate, zinc acetate, zinc chloride, 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.
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.
Aging temperature described in step (2) is 30~85 DEG C, preferably 40~80 DEG C；Ageing time be 1~for 24 hours, preferably 2
~16h.
Crystallization temperature described in step (2) is 120~210 DEG C, preferably 130~185 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 10~96h, preferably 24~72h.
420~780 DEG C of calcination temperature described in step (3), preferably 450~650 DEG C；1~8h of roasting time；Exchange examination
Agent 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%.
By the present invention isomerization catalyst be used for normal octane hydroisomerization reaction, 180~450 DEG C, 0.5~
4.2MPa, WHSV=0.8~8h-1Under the conditions of hydrogen to oil volume ratio 80~450, normal octane conversion ratio is above 88%, and isomery is pungent
Alkane is selectively even more that 85.06% is up at 200 DEG C.
Compared with prior art, the present invention has the following advantages：
1, the isomerization catalyst obtained by the present invention is used into mesoporous Zn-ZSM-5 molecular sieves or improved mesoporous Zn-
ZSM-5 molecular sieve, base metal greatly slow down catalyst metals activity as hydrogenation-dehydrogenation metal active centres component
Center 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, and the activity and selectivity of catalyst is improved simultaneously.
2, 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, and carbon deposition rate is low.
3, 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.
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 molecular sieve that the embodiment of the present invention 1 is prepared
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 of molar ratio 40.
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) 0.44g NaAlO are weighed2With 2.14g Zn (NO3)2·6H2O is dissolved in 49.55g deionized waters, is then added dropwise
0.93g TMA are added after stirring 5min in 2.00g sulfuric acid (3mol/L), and 14.20g waterglass is added (containing 27.6wt% after stirring 1h
SiO2, the Na of 7.1wt%2The H of O and 65.3wt%2O), 2h is mixed at room temperature, a mole group for mixture becomes
0.003Al2O3:0.25Na2O:1SiO2:50H2O:0.24SDA:0.11ZnO。
(2) mixture that step (1) obtains is warming up to 75 DEG C of aging 6h, then poured this solution into band polytetrafluoroethylene (PTFE)
In the stainless steel crystallizing kettle of lining, 130 DEG C of crystallization 12h are warming up to, then heat to 180 DEG C of static crystallization for 24 hours.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.
(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, can prove that the sample synthesized is the Zn-ZSM-5 of high-purity by XRD spectra (Fig. 1)
Molecular sieve；By N2It is double that adsorption/desorption isotherms (Fig. 2) and graph of pore diameter distribution (Fig. 3) prove that the Zn-ZSM-5 molecular sieves of synthesis have
The meso-hole structure of hysteresis loop distribution, mesoporous pore size concentrate on 5~30nm, specific surface area 580m2/g；NH3- TPD spectrograms (Fig. 4)
Prove that 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 480
DEG C, show that the Zn-ZSM-5 molecular sieves of synthesis have significant lower acid strength, total acid content low compared with business ZSM-5 molecular sieve
20%, and the catalyst anti-carbon deposition ability prepared is strong.Then the ZnO that impregnating effect score is 5% again.
2, Ni-Mo/Zn-ZSM-5 catalyst is prepared
By the above-mentioned Zn-ZSM-5 molecular sieves handled well of 30g, it is uniformly mixed with 15g aluminium oxide and 20g deionized waters, then
Extruded moulding, the dry 4h at 120 DEG C, 550 DEG C of roasting 5h obtain molecular sieve carrier, then multiple maceration are used to impregnate
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
0.02Al2O3:0.06Na2O:1SiO2:15H2O:0.03SDA:0.002ZnO。
(2) aging condition：50 DEG C, 8h；Crystallization condition：120 DEG C of crystallization 12h, for 24 hours, 170 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) binder is kaolin, and 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 0.04Al2O3:0.15Na2O:1SiO2:30H2O:
0.15SDA:0.06ZnO。
(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 6-12nm, and 25%) 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) binder is magnalium hydrotalcite, and 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 0.05Al2O3:0.12Na2O:1SiO2:20H2O:
0.05SDA:0.01ZnO。
(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 10-20nm, and 32%) 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
0.015Al2O3:0.20Na2O:1SiO2:40H2O:0.09SDA:0.04ZnO.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 1:1.5 being added after 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 provides a kind of Ni-Mo/Zn-ZSM-5 catalyst, and preparation process is with embodiment 1, only in modulation step 2
The preparation of catalyst, it is specific as follows：
(1) it by the above-mentioned Zn-ZSM-5 molecular sieves handled well of 28g, is uniformly mixed with 13g aluminium oxide and 16g deionized waters,
Then extruded moulding, the dry 4h at 120 DEG C, 600 DEG C of roasting 5h obtain molecular sieve carrier, then multiple maceration are used to soak
The MoO of the NiO and 4.5wt% of stain 7.0wt%3, Ni-Mo/Zn-ZSM-5 catalyst is made.
Embodiment 7
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 200 DEG C, collect reaction product and analyzed.It protects in the whole process
It is 10g/h, system pressure 2.0MPa, hydrogen to oil volume ratio 300 to hold normal octane feed rate.Catalysis reaction result is shown in Table 1.
Embodiment 8
The present embodiment, by catalyst for fixed bed reaction test activity, step exists with embodiment 7, parameter difference
In：Catalyst is the catalyst that embodiment 2 obtains, and reaction temperature is 250 DEG C.
Embodiment 9
The present embodiment, by catalyst for fixed bed reaction test activity, step exists with embodiment 7, parameter difference
In：Catalyst is the catalyst that embodiment 3 obtains, and reaction temperature is 300 DEG C.
Embodiment 10
The present embodiment, by catalyst for fixed bed reaction test activity, step exists with embodiment 7, parameter difference
In：Catalyst is the catalyst that embodiment 4 obtains, and reaction temperature is 280 DEG C.
Embodiment 11
The present embodiment, by catalyst for fixed bed reaction test activity, step exists with embodiment 7, parameter difference
In：Catalyst is the catalyst that embodiment 5 obtains, and reaction temperature is 260 DEG C.
Embodiment 12
The present embodiment, by catalyst for fixed bed reaction test activity, step exists with embodiment 7, parameter difference
In：Catalyst is the catalyst that embodiment 6 obtains, and reaction temperature is 250 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 7, 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 8.
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 7 | 88.60 | 85.06 | 14.36 | 0.18 |
| Embodiment 8 | 91.03 | 86.19 | 13.20 | 0.20 |
| Embodiment 9 | 95.68 | 88.69 | 11.01 | 0.24 |
| Embodiment 10 | 92.55 | 87.31 | 12.33 | 0.15 |
| Embodiment 11 | 90.94 | 89.52 | 10.12 | 0.25 |
| Embodiment 12 | 88.54 | 83.79 | 15.53 | 0.42 |
| Comparative example 2 | 99.18 | 3.56 | 95.27 | 1.12 |
| Comparative example 3 | 96.67 | 70.28 | 28.31 | 0.95 |
As it can be seen from table 1 catalyst provided by the invention has excellent isomerization reaction activity, compared with comparative example
With higher isoparaffin selectivity and lower cracking rate (i.e. high liquid yield) and coking yield.Described in embodiment 9
Under conditions of, stability experiment has been carried out to catalyst, the results showed that after reacting 1000h, the conversion ratio and isomery of catalyst
Body is selectively kept at 90.0,88.5% or more, and cracking rate and coking yield are respectively lower than 10.5,0.28%.Therefore, this hair
The catalyst of bright offer has more excellent isomerization ability, has good economic benefit and prospects for commercial application.
Claims (10)
1. a kind of isomerization catalyst, it is characterised in that：By weight percentage, including the mesoporous Zn-ZSM-5 of 30 ~ 85%H types divides
Son sieve or improved mesoporous Zn-ZSM-5 molecular sieves, 8 ~ 56% aluminium oxide, magnalium hydrotalcite and/or Kaolin binder, dipping
0.2 ~ 14% metal active constituent, the metal active constituent are one or more of Fe, Co, Ni, Mo, W.
2. isomerization catalyst according to claim 1, it is characterised in that：The mesoporous Zn-ZSM-5 molecules of the H-type
Sieve, mesoporous pore size concentrate on 4-35 nm, and specific surface area is 350-680 m2/ g, zinc oxide content are the 0.2 of molecular sieve total weight
~9.5%。
3. isomerization catalyst according to claim 1, it is characterised in that：The improved mesoporous Zn-ZSM-5 molecules
Sieve, mesoporous pore size concentrate on 4-35 nm, and specific surface area is 350-680 m2/ g, zinc oxide content are the 0.2 of molecular sieve total weight
~ 9.5%, molecular sieve surface Zn content is higher than Zn content inside molecular sieve.
4. wanting the isomerization catalyst described in 3 according to right, it is characterised in that：The improved mesoporous Zn-ZSM-5 molecular sieves table
Face Zn content is 0.2 ~ 2 times higher than Zn content inside molecular sieve.
5. a kind of preparation method of isomerization catalyst as described in claim 1, it is characterised in that：It includes the following steps：
The mesoporous Zn-ZSM-5 molecular sieves of H-type or improved Zn-ZSM-5 molecular sieves are glued with aluminium oxide, magnalium hydrotalcite and/or kaolin
Agent mixed-forming is tied, then impregnates base metal active component and roasts and obtain isomerization catalyst.
6. the preparation method of isomerization catalyst according to claim 5, it is characterised in that：The mesoporous Zn- of the H-type
The preparation method of ZSM-5 molecular sieve, includes the following steps：
(1) at a certain temperature, deionized water, silicon source, zinc source, acid source, template SDA and silicon source are mixed under agitation
It is uniformly prepared into gel, adjusting molar ratio of material is (0.002 ~ 0.06) Al2O3: (0.04~0.25)Na2O: 1SiO2: (10~
50)H2O: (0.02~0.25)SDA: (0.001~0.12)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；
(3) it is mesoporous to be obtained into H-type through exchange, filtering, drying, calcination process for the Zn-ZSM-5 molecular sieves obtained in step (2)
Zn-ZSM-5 molecular sieves.
7. the preparation method of isomerization catalyst according to claim 6, it is characterised in that：The improved Zn-ZSM-5
The preparation method of molecular sieve is as follows：It will obtain the mesoporous Zn-ZSM-5 molecular sieves of H-type and impregnate zinc compound again modifying so that
Molecular sieve surface Zn content is higher than Zn content inside molecular sieve.
8. the preparation method of isomerization catalyst according to claim 6, it is characterised in that：Step (1) source of aluminium is
One or more of sodium metaaluminate, aluminium isopropoxide, aluminum sulfate；The silicon source be waterglass, Ludox, ethyl orthosilicate,
One or more of solid silicone；The zinc source is one or more of zinc nitrate, zinc acetate, zinc chloride, zinc sulfate.
9. the preparation method of isomerization catalyst according to claim 6, it is characterised in that：Step (1) described silicon source is
One or both of diatomite, opal, silicon source are one or more of kaolin, rectorite, perlite, montmorillonite,
Zinc source is one or both of smithsonite, zincite.
10. the preparation method of isomerization catalyst according to claim 6, which is characterized in that the crystallization described in step (2)
Temperature is 120 ~ 210 DEG C, divides 1 ~ 5 section to be segmented not isothermal heating treatment, first quick and back slow, 100 DEG C in the past with 6 for heating rate
The heating rate of ~ 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 hour；100~
It is heated up with the heating rate of 3 ~ 5 DEG C/min between 200 DEG C, 10 ~ 20 DEG C are a warming-up section, and temperature section processing time is
0.5 ~ 8 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810251965.6A CN108452840B (en) | 2018-03-26 | 2018-03-26 | Isomerization catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810251965.6A CN108452840B (en) | 2018-03-26 | 2018-03-26 | Isomerization catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108452840A true CN108452840A (en) | 2018-08-28 |
| CN108452840B CN108452840B (en) | 2020-07-07 |
Family
ID=63237926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810251965.6A Active CN108452840B (en) | 2018-03-26 | 2018-03-26 | Isomerization catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108452840B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111111758A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Catalyst for preparing toluene and/or xylene by liquid-phase methylation and preparation method thereof |
| CN111185226A (en) * | 2020-03-06 | 2020-05-22 | 中化泉州石化有限公司 | Preparation method of Zn modified molecular sieve loaded Ni/W bimetal heterogeneous pour point depressing catalyst |
| CN111905800A (en) * | 2019-05-10 | 2020-11-10 | 中国石油天然气股份有限公司 | Molybdenum-containing and nickel-or/and zinc-containing ZSM-5 molecular sieve with multi-stage structure, and preparation method and application thereof |
| CN112007652A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Solid acid catalyst and application thereof |
| CN114433212A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Protective catalyst for aromatic hydrocarbon transalkylation reaction and preparation method and application thereof |
| CN115770594A (en) * | 2021-09-06 | 2023-03-10 | 浙江省化工研究院有限公司 | Preparation method and application of hydrophobic catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525246A (en) * | 2015-01-22 | 2015-04-22 | 厦门大学 | Preparation method and application of no-template-agent small-grain Zn-ZSM-5 catalyst |
| CN104607235A (en) * | 2015-01-13 | 2015-05-13 | 大连理工大学 | Preparation method of Zn-ZSM-5 and application of Zn-ZSM-5 in preparing propylene via propane dehydrogenation |
| CN106830001A (en) * | 2017-03-14 | 2017-06-13 | 中国矿业大学 | A kind of synthetic method of the molecular sieves of c axial directions Zn ZSM 5 with meso-hole structure |
-
2018
- 2018-03-26 CN CN201810251965.6A patent/CN108452840B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607235A (en) * | 2015-01-13 | 2015-05-13 | 大连理工大学 | Preparation method of Zn-ZSM-5 and application of Zn-ZSM-5 in preparing propylene via propane dehydrogenation |
| CN104525246A (en) * | 2015-01-22 | 2015-04-22 | 厦门大学 | Preparation method and application of no-template-agent small-grain Zn-ZSM-5 catalyst |
| CN106830001A (en) * | 2017-03-14 | 2017-06-13 | 中国矿业大学 | A kind of synthetic method of the molecular sieves of c axial directions Zn ZSM 5 with meso-hole structure |
Non-Patent Citations (2)
| Title |
|---|
| K. SHARIFI,ET.AL: "Investigation of the effect of HZSM‑5 over HDS and reforming processes for clean gasoline production", 《INTERNATIONAL JOURNAL OF ENVIRONMENTAL SCIENCE AND TECHNOLOGY》 * |
| 张雄福: "杂原子Zn-ZSM-5沸石分子筛合成及影响因素研究", 《大连理工大学学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111111758A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Catalyst for preparing toluene and/or xylene by liquid-phase methylation and preparation method thereof |
| CN111111758B (en) * | 2018-10-30 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst for preparing toluene and/or xylene by liquid phase methylation and preparation method thereof |
| CN111905800A (en) * | 2019-05-10 | 2020-11-10 | 中国石油天然气股份有限公司 | Molybdenum-containing and nickel-or/and zinc-containing ZSM-5 molecular sieve with multi-stage structure, and preparation method and application thereof |
| CN112007652A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Solid acid catalyst and application thereof |
| CN111185226A (en) * | 2020-03-06 | 2020-05-22 | 中化泉州石化有限公司 | Preparation method of Zn modified molecular sieve loaded Ni/W bimetal heterogeneous pour point depressing catalyst |
| CN114433212A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Protective catalyst for aromatic hydrocarbon transalkylation reaction and preparation method and application thereof |
| CN114433212B (en) * | 2020-10-19 | 2023-09-29 | 中国石油化工股份有限公司 | Protection type catalyst for arene alkyl transfer reaction, and preparation method and application thereof |
| CN115770594A (en) * | 2021-09-06 | 2023-03-10 | 浙江省化工研究院有限公司 | Preparation method and application of hydrophobic catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108452840B (en) | 2020-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108452840A (en) | A kind of isomerization catalyst and preparation method | |
| CN108435235A (en) | A kind of mesoporous Zn-ZSM-5 molecular sieves and low cost preparation method | |
| CN101596462B (en) | Hydroisomerizaion catalyst and preparation method thereof | |
| CN108219841B (en) | A kind of method for cleaning of catalytic gasoline of whole fraction | |
| CN109772443A (en) | A kind of molecular sieve carried high dispersive Pt catalyst of ZSM-12 and preparation method thereof | |
| CN107265478B (en) | A kind of boron modification ferrierite molecular sieve catalyst and the preparation method and application thereof | |
| CN102119123A (en) | Catalyst comprising an IZM-2 zeolite and at least one metal and use thereof in the conversion of hydrocarbons | |
| CN103769104B (en) | Nickel system selective hydrocatalyst, its preparation method and application | |
| CN104148107B (en) | A kind of Catalysts and its preparation method being transformed diesel oil distillate processed by synthesis gas one step | |
| CN109092352A (en) | A kind of FCC gasoline polymerization catalyst and preparation method | |
| CN104549480A (en) | Binder-free SAPO-34/ZSM-5 composite molecular sieve based catalyst as well as preparation method and application thereof | |
| CN101530813A (en) | Method for preparing molecular sieve catalyst used in carbon 4 liquid gas aromatization reaction | |
| CN102513143A (en) | Preparation method of catalyst for catalyzing aromatization modification of gasoline | |
| CN109806910A (en) | A kind of molecular sieve carried high-dispersion metal catalyst of H-type EUO and preparation method thereof | |
| CN112371167B (en) | Catalyst for producing high-octane component gasoline and preparation method and application thereof | |
| CN108993585A (en) | A kind of bifunctional catalyst and preparation method thereof of the molecular sieve of EUO containing multi-stage porous | |
| CN104549483A (en) | Adhesive-free SAPO-34/ZSM-5 composite molecular sieve and preparation method thereof | |
| CN101318141B (en) | Hydroisomerization catalyst, preparation and application thereof | |
| CN104107716A (en) | Catalyst for aromatization of C6-C8 normal paraffins, and preparation and application thereof | |
| CN105800632A (en) | Small crystal grain stepwise pore SAPO-11 molecular sieve and hydrocarbon isomerization catalyst and their preparation methods | |
| CN107970933A (en) | A kind of three selective hydrogenation catalyst of carbon, preparation method and method of hydrotreating | |
| CN105126899A (en) | Poor-quality heavy oil suspended bed hydrogenation catalyst supported on molecular sieve, preparation method and use method thereof | |
| CN102895991A (en) | Method for preparing fluid catalytic cracking (FCC) gasoline small-molecule sulfur densification catalyst | |
| AU2007233022A1 (en) | Hydrocracking catalyst and process for producing fuel substrate | |
| CN108262060A (en) | A kind of gasoline catalyzing and olefine reducing aromatized catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |