CN106824261B - Ni-SSZ-13 catalyst, preparation method and its usage - Google Patents
Ni-SSZ-13 catalyst, preparation method and its usage Download PDFInfo
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Abstract
The present invention relates to Ni-SSZ-13 catalyst, preparation method and its usage, the technical problem that the preparation cost for mainly solving SSZ-13 material in the prior art is expensive, nickel-loaded metal dispersion is uneven and the stability of methanol-to-olefin catalyst is not high, catalytic activity is not high, the present invention is by using a kind of Ni-SSZ-13 catalyst, based on parts by weight, including following components: (1) 0.1~20 part of Ni or its oxide；(2) 80~99.9 parts of SSZ-13 molecular sieve, preferably solves the problems, such as this, in the industrial production that can be used for adding hydrogen, hydrocarbon cracking and methanol-to-olefins.
Description
Technical field
The present invention relates to a kind of Ni-SSZ-13 catalyst, preparation method and its usage, more particularly to one kind with nickel amine chela
Close method of the object as template (guiding) agent synthesizing Si-Al type CHA molecular screen material.
Background technique
Since interior bore size distribution ranges are wide and the rich and varied property of topology, zeolite molecular sieve material are wide
It is applied generally in fields such as absorption, heterogeneous catalysis, the carrier of all kinds of guest molecules and ion exchanges.They are with selective absorption
For main feature, unique pore canal system makes it have the ability for sieving different sized molecules, this is also that this kind of material is claimed
Be " molecular sieve " the reason of.Theoretically only has the material of adsorption capacity (guest molecule water or template can be removed)
It can be referred to as poromerics or molecular sieve.According to international pure and applied chemistry federation (IUPAC) definition, porous material
Following three classes can be divided by their bore dia: material of the aperture less than 2nm is poromerics (micropore
materials)；Aperture is mesoporous material (mesopore materials) 2 to the material between 50nm；Aperture is greater than 50nm
Material be large pore material (macropore materials), zeolite molecular sieve channel diameter is generally in 2nm hereinafter, therefore quilt
It is classified as poromerics.
Early stage zeolite refers to alumino-silicate, it is by SiO4Tetrahedron and AlO4Tetrahedron is basic structural unit, passes through bridge
One kind that oxygen connects and composes has the containing Microporous Compounds of cage type or cellular structure.The forties in last century, Barrer etc. is for the first time in reality
Test the artificial zeolite for having synthesized in room and being not present in nature, hereafter into ten Yu Nianli, Milton, Breck and Sand etc.
Alkali or alkaline earth metal hydroxide is added using hydrothermal technique in people in aluminosilicate gels, synthesized A type, X-type, L-type,
Y-type zeolite and modenite etc.；Nineteen sixties, with the introducing of organic base cation, a series of brand news
Zeolite molecular sieve is prepared out, such as serial (ZSM-1, ZSM-5, ZSM-11, the ZSM-22, ZSM-48) zeolite molecules of ZSM-n
Sieve, this kind of molecular sieve have many advantages, such as preferable catalytic activity, hydrothermal stability and higher corrosion resistance, are widely used
In fields such as PETROLEUM PROCESSING, fine chemistry industries, it always is the hot spot of research for many years.It is sieved in numerous ZSM-n Series Molecules
In, ZSM-5 is most widely used, it is the zeolite molecular sieve of Pentasil type two-dimensional channel system, by ten yuan of ellipse
Ring straight hole road (0.54nm × 0.56nm) and sinusoidal duct (0.51nm × 0.54nm) composition.ZSM-5 zeolite has excellent urge
Change performance, is widely used in the very important industrial chemical process such as catalytic cracking, aromatisation, alkylation, disproportionation.
Nineteen eighty-two, the scientist Wilson S.T. and Flanigen E.M. etc. of American Association Carbide (UCC company)
A completely new molecular sieves are successfully synthesized and had developed using silicon source, phosphorus source and organic formwork agent --- aluminum phosphate
Molecular sieve-4 A lPO4- n, n represent model (US4310440).After 2 years, UCC company is in AlPO4On the basis of-n, Si original is used
Subdivision substitutes the Al atom and P atom in AlPO skeleton, has been successfully prepared out another serial silicoaluminophosphamolecular molecular sieves SAPO-
N, n represent model (US4440871, US4499327).For SAPO-34 molecular sieve as important a member in SAPO-n, structure is similar
Chabasie belongs to cubic system.SAPO-34 skeleton primitive is by AlO4、SiO4And PO4Tetrahedron forms, and includes in skeleton
The three dimensional intersection structure of elliposoidal supercage and 8- person's annular distance road, 8- person's annular distance road aperture are about 0.38nm, and supercage aperture is straight
Diameter is maintained between 0.43~0.50nm, topology symbol CHA.SAPO-34 molecular sieve is because having suitable Bronsted acidity, larger
Specific surface area, preferable absorption property, preferable thermal stability, good hydrothermal stability and cellular structure to low-carbon alkene
Hydrocarbon selects that type is selectively splendid etc., makes it as the catalyst of preparing light olefins from methanol (MTO) for showing in the reaction
Good catalytic activity and selectivity.
The chemist Zones of nineteen eighty-three Chevron Corporation (Stardard Oil Company of California) is in N, N, the organic sun of N- trimethyl -1- amantadine (TMAA+) from
Son is as having synthesized a kind of new Si-Al molecular sieve SSZ-13 (United States Patent (USP) No.4544538) under conditions of structure directing agent.This
Kind of molecular sieve is also that (AlPO-34 and SAPO-34 are respectively the aluminium phosphate molecular sieve and silicon phosphate of CHA structure for a kind of chabasie
Aluminum molecular screen), since such molecular sieve has good thermal stability, it can be used as the carrier of adsorbent or catalyst, such as empty
Gas cleanser, auto-exhaust catalyst etc..SSZ-13 molecular sieve also has cationic exchangeability and acid adjustability simultaneously, thus
There is good catalytic performance to kinds of reaction, catalytic cracking including hydrocarbon compound, be hydrocracked and alkene and
Aromatic hydrocarbons construction reaction etc..
It is mentioned in the application specification of the patent No.60826882 of Zones application in 2006, he, which has found a kind of reduce, makes
Use the dosage of TMAA+ as the method for the synthesis SSZ-13 molecular sieve of structure directing agent.By be added benzyl quaternary ammonium ion and
TMAA+ cation can significantly reduce the dosage of TMAA+ cation together as the structure directing agent of reactant.Although this
Kind synthetic method effectively reduces cost but is related to the problem using expensive TMAA+ cation.When evening in the same year is a little
Between, a kind of benzyl trimethyl quaternary ammonium ion is proposed in the application specification for the patent No.60882010 that Miller is submitted
(BzTMA+) N, N, conjunction of the N- trimethyl -1- amantadine cation as the SSZ-13 molecular sieve of structure directing agent are partially replaced
At method.
Hydro-thermal, the method for solvent-thermal process is usually used in above-mentioned sial, phosphorus aluminium and corresponding hetero-atom molecular-sieve
Preparation.It may be said that hydro-thermal, solvent-thermal process method are the method for the most frequently used synthesis of molecular sieve, typical a hydro-thermal, solvent heat
Having main steps that for synthetic method first uniformly mixes the reactions such as silicon source (phosphorus source), silicon source, structure directing agent, alkali and water (solvent)
It closes, obtains starting sol i.e. crystallization mixture, then which is placed in polytetrafluoroethylene (PTFE) is liner, stainless steel is again
In the reaction kettle of outer wall, crystallization is carried out at certain temperature and self-generated pressure after closed, such as the process of earth lithogenesis.
For reactant, the silicon source of synthesizing Si-Al, phosphorus aluminium and corresponding hetero-atom molecular-sieve generally can with silica solution, silica gel,
Sodium metasilicate, White Carbon black and organosilicon etc., silicon source generally use aluminum sulfate, aluminum nitrate, sodium metaaluminate, alumina sol, organo-aluminium
And boehmite etc., alkali can be in the general orthophosphoric acid of phosphorus source, monoammonium phosphate, ammonium dihydrogen phosphate or diammonium hydrogen phosphate
Machine alkali, ammonium hydroxide, NaOH, KOH etc..The use of template plays a crucial role in the synthesis process of molecular sieve, both may be used
To be the alkali metal cations such as sodium, potassium, it is also possible to the organic molecules such as organic quaternary ammonium salt, crown ether.With regard to current document report
Speech, it is 3-50, synthetic system single solvent heat seal that prior synthesizing method, which prepares SSZ-13 molecular sieve sieve and silica-sesquioxide ratio range,
At be related to organic formwork agent that is less and relating generally to be amantadine, Kui core alcohol and 2- outside-aminonorbornane, such mould
Plate agent is not only expensive, is difficult to synthesize, and high temperature high fever ability burn off is needed in the treatment process in later period, and the above problem is big
The process of its industrial application is constrained greatly.
Bis- (cyclopentadienyl) is used early in the early 1990s in last century K.J.Balkus, Jr. et al.
Cobalt (III) ion synthesizes nonasil molecular sieve (NON) as template.First super large 14- person's ring UTD-1 in 1996
Successful synthesis make scientific research personnel fully recognize a kind of new type template --- metallo-chelate has work successively later
Metallo-chelate made reports as template synthesizing P-Al molecular sieve, plurality of AlPO4Framework of molecular sieve structure is closed
At such as AFI, CHA, GTex-2, GTex-3 etc..It is worth mentioning that Xu Ruren research group, Jilin University is with metal complex
The trbasic zinc phosphate, phosphoric acid gallium and vanadium phosphate compound of a large amount of novel structures are prepared for as organic formwork agent.
Summary of the invention
The first technical problem to be solved by the present invention is that the preparation cost of SSZ-13 material in the prior art is expensive, loads
Nickel metal dispersion is uneven and catalyst stability is not high, urges in the reaction of methanol-to-olefins, hydrogenation reaction or hydrocarbon cracking
Change the not high technical problem of activity, a kind of Ni-SSZ-13 catalyst is provided, which has preparation cost cheap, gold-supported
Belong to and being highly dispersed inside duct and catalytic activity height and the high advantage of stability.
The second technical problem to be solved by the present invention is to provide one kind and is closed using nickel amine chelate as template (guiding) agent
At the preparation method of sial type CHA molecular screen material.
The third technical problem to be solved by the present invention provide a kind of Ni-SSZ-13 catalyst material be used to prepare alkene or
The purposes of Downstream Products of Methanol.
One of to solve above-mentioned technical problem, technical scheme is as follows: a kind of Ni-SSZ-13 catalyst, with weight
Number meter is measured, including following components: (1) 0.1~20 part of Ni or its oxide；(2) 80~99.9 parts of SSZ-13 molecular sieve.
In above-mentioned technical proposal, it is preferred that the content of Ni or its oxide is 0.5~18 part；It is furthermore preferred that Ni or its oxygen
The content of compound is 2~16 parts；It is furthermore preferred that the content of Ni or its oxide is 4~12 parts；It is furthermore preferred that Ni or its oxidation
The content of object is 6~10 parts.
In above-mentioned technical proposal, it is preferred that catalyst passes through fabricated in situ.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: it is a kind of using nickel amine chelate as
The preparation method of template (guiding) agent synthesizing Si-Al type CHA molecular screen material, it is characterised in that first by nickel amine chelate or nickel
Salt, chelating agent are added in configured silicon source solution, are sufficiently stirred, and inorganic base regulation system pH value is added in whipping process
Between 7~12, continue silicon source needed for stirring certain time and being added, continues stirring to forming uniform crystallization mixture, it
Crystallization mixture is fitted into the stainless steel cauldron with polytetrafluoroethylene (PTFE) afterwards, 100~200 DEG C at a temperature of crystallization 5h~
10 days；After the completion of crystallization, crystallization product is sufficiently washed with ethyl alcohol, acetone and deionized water respectively, and 60~100
DEG C dry 4~24 hours；By the exchange of ammonium ion for several times and after 400~600 DEG C of roasting a few hours, final products are obtained.
In above-mentioned technical proposal, it is preferred that the preparation method of catalyst comprises the following steps:
A, with raw materials used molar ratio Al2O3: SiO2: nickel amine chelate: solvent: OH-It is 1: 1~500: 1~500:
10~1000: 1~100, silicon source and solvent are sufficiently stirring and mixing to form solution A first；
B, nickel salt, chelating agent and/or nickel amine chelate are added in solution A and are sufficiently stirred, and be added in whipping process
Inorganic base regulation system pH value forms solution A between 7~121；
C, A is added in silicon source needed for reaction1Uniform crystallization mixture A is formed after being sufficiently stirred in solution2；
D, by crystallization mixture A2Crystallization 5h~10 day obtain crystallization product at a temperature of 100~200 DEG C；
E, final products will be obtained after crystallization product washing, drying and roasting.
In above-mentioned technical proposal, preferred technical solution is raw materials used molar ratio are as follows: Al2O3: SiO2: nickel amine chela
Close object: solvent: OH-It is 1: 3~300: 2~200: 30~600: 2~80.
Preferred technical solution is raw materials used molar ratio are as follows: Al2O3: SiO2: nickel amine chelate: solvent: OH-It is 1
: 5~200: 5~120: 100~400: 5~50.
Preferred technical solution is raw materials used molar ratio are as follows: Al2O3: SiO2: nickel amine chelate: solvent: OH-
It is 1: 10~100: 10~60: 150~300: 8~40.
Sulfate of the nickel source of nickel amine chelate selected from nickel in above-mentioned technical proposal, nitrate, carbonate, in acetate
It is a kind of；Chelating agent is selected from ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, 1,10- Phen, 2,2- and joins pyrrole
At least one of pyridine or 4,4- bipyridyl；Solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, ethyl alcohol, second two
At least one of alcohol or deionized water.
Preferred technical solution is at least one of chelating agent in diethylenetriamine, triethylene tetramine, tetraethylenepentamine
Kind, solvent is at least one of n,N-Dimethylformamide, ethyl alcohol or deionized water；Preferred technical solution is selected from for silicon source
At least one of aluminate, meta-aluminate, the hydroxide of aluminium, the oxide of aluminium or mineral containing aluminium；Silicon source is selected from organic
At least one of silicon, amorphous silica, silica solution, solid oxidation silicon, silica gel, diatomite or waterglass；Inorganic base is
At least one of hydroxide of alkali or alkaline earth metal.
Preferred technical solution is that silicon source is selected from least one of aluminate or meta-aluminate；Silicon source is selected from amorphous
At least one of silica, silica solution or solid oxidation silicon；Inorganic base is LiOH, NaOH or KOH at least one.
In above-mentioned technical proposal in step d by crystallization mixture 120~180 DEG C at a temperature of crystallization 12 hours~6 days.
To solve above-mentioned technical problem three, The technical solution adopted by the invention is as follows: using nickel amine chelate as template
(guiding) agent synthesizing Si-Al type CHA molecular screen material is catalyst, and the catalysis reaction of hydro carbons is prepared for methanol.
In above-mentioned technical proposal, the application method of Ni-SSZ-13 catalyst is as follows: above-mentioned Ni-SSZ-13 catalyst is not
Application in saturated compounds or high molecular hydrogenation with unsaturated bond；It is furthermore preferred that catalyst is suitable for cracking
The hydrogenation process of unsaturated component in carbon nine and its above hydrocarbon-fraction.
In above-mentioned technical proposal, the application method of Ni-SSZ-13 catalyst is as follows: above-mentioned Ni-SSZ-13 catalyst is in hydrocarbon
Application in class cracking reaction；Preferably, cracking reaction reaction condition are as follows: 500~650 DEG C of reaction temperature, diluent/raw material weight
Amount ratio 0~1: 1, liquid phase air speed 1~30 hour-1, reaction pressure -0.05~0.2MPa.Hydro carbons includes preferably at least one alkene
Hydrocarbon more preferably includes at least one C4 and the above alkene.
In above-mentioned technical proposal, the application method of Ni-SSZ-13 catalyst is as follows: above-mentioned Ni-SSZ-13 catalyst is in first
Application in alcohol hydrocarbon reaction；Preferably, methanol conversion prepares the reaction condition of hydro carbons are as follows: using methanol as raw material, is reacting
Temperature is 400~600 DEG C, and reaction pressure is 0.01~10MPa, and methanol weight air speed is 0.1~15h-1。
Content containing metallic element Ni in Ni-SSZ-13 molecular sieve is in plasma P erkin-Elmer 3300DV
It is measured on icp analysis instrument, the specific operation method is as follows:
Sample is placed in 100 DEG C of baking ovens to dry 2 hours, 0.2~0.5g of sample after weighing drying later in platinum crucible or
In King crucible, add 10 drop volumes than the sulfuric acid solution for 1:1 with 8mL hydrofluoric acid, heating often shakes and accelerates sample point
Solution is steamed to white cigarette and is emitted to the greatest extent, removed cooling, add 1:1 hydrochloric acid 5mL and suitable quantity of water after solution in crucible is thorough clearly by solution.It heats molten
Solve residue, then move into 100mL volumetric flask, be eluted with water crucible and it is dilute to scale and shake up, configured solution is introduced
ICP spectrometer analysis records percentage composition.
Sial type CHA molecular screen material prepared by the present invention has wide silica alumina ratio adjustable extent, heat and hydrothermally stable
Property relatively strong, preparation system diversification and roasting after product metal ion high degree of dispersion the characteristics of, for methanol conversion system
The reaction process of hydrocarbon, within the scope of the evaluation condition of setting, methanol conversion 100%, the one way receipts of product ethylene and propylene
Rate reaches as high as 85.9%, while catalyst is with good stability, achieves preferable technical effect.
The present invention is further elaborated below by embodiment.
Detailed description of the invention
Fig. 1 be Ni-SSZ-13 XRD diffracting spectrum (wherein SSZ-13 molecular sieve 2 θ be 9.53 ± 0.02,12.92 ±
0.05,14.01 ± 0.05,16.05 ± 0.02,17.89 ± 0.05,20.65 ± 0.05,23.17 ± 0.1,25.06 ± 0.01,
There is diffraction maximum at 26.01 ± 0.02,27.94 ± 0.1,30.73 ± 0.1,34.58 ± 0.02)
Specific embodiment
[embodiment 1]
Synthesis of the nickel amine chelate as template (guiding) agent synthesizing Si-Al type CHA molecular screen material.
Weigh the aluminum nitrate [Al (NO of 86.98g3)3·9H2O, 0.23mol] it is dissolved in 269.1mL deionized water, stirring is equal
After even, it is added 178.52g Ni-TEPA chelate (being made by nickel salt and tetraethylenepentamine, n (Ni:TEPA=1:1)), sufficiently stirs
After mixing, above-mentioned solution is added in the sodium hydroxide of 49.57g [NaOH, 1.05mol] later and adjusts solution ph between 7~8,
162.5g silica solution [SiO is added under stirring2, 30wt%, 0.84mol], closed strong stirring is to being uniformly mixed, to complete
Crystallization mixture is placed in in the pressure vessel of polytetrafluoroethylene (PTFE) lining the crystallization 12h at 180 DEG C, product process after mixing
After filter, washing, 80 DEG C of dry 12h after washing then heat to 600 DEG C, and constant temperature calcining 6h both obtains product, is denoted as NS-1, the body
The reactant stoichiometric ratio of system is as follows: Al2O3: SiO2: nickel amine chelate: solvent: OH-=1: 3.65: 4.57: 65: 2.26,
Show that Ni content and SSZ-13 molecular sieve content are listed in table 1 through ICP test, the XRD diffracting spectrum of product NS-1 is shown in Fig. 1.
[embodiment 2]
Synthesis of the nickel amine chelate as template (guiding) agent synthesizing Si-Al type CHA molecular screen material.
Weigh the aluminum sulfate [[Al of 2211.98g2(SO4)3·18H2O, purity >=98wt.%, 3.32mol] it is dissolved in
In 21219.6mL deionized water and 1230.6mL n,N-Dimethylformamide [DMF] after mixing evenly, 651.66g sulphur is added
Sour nickel [NiSO4·6H2O, 8.28mol] and 365.5g triethylene tetramine [TETA, 2.5mol] be sufficiently stirred, later will
The lithium hydroxide [LiOH, 4.97mol] of 198.75g is added above-mentioned solution and adjusts solution ph between 9~10, under stirring
19836.4g silica solution [SiO is added2, 40wt%, 132.24mol], closed strong stirring is to being uniformly mixed, wait be thoroughly mixed
Crystallization mixture is placed in the pressure vessel that polytetrafluoroethylene (PTFE) serves as a contrast the crystallization 3d at 160 DEG C after even, product is through being filtered, washed
Afterwards, 100 DEG C of dry 8h after washing then heat to 500 DEG C, and constant temperature calcining 8h both obtains product, is denoted as NS-2, the reaction of the system
Object stoichiometry ratio is as follows: Al2O3: SiO2: nickel amine chelate: solvent: OH-=1: 39.83: 1.51: 360.15: 2.56, warp
ICP test shows that Ni content and SSZ-13 molecular sieve content are listed in table 1.
[embodiment 3]
Synthesis of the nickel amine chelate as template (guiding) agent synthesizing Si-Al type CHA molecular screen material.
Weigh the sodium aluminate [NaAlO of 6.18g2, 0.08mol] and it is dissolved in 49.1mL deionized water, after mixing evenly, it is added
8.92g nickel nitrate [Ni (NO3)2·6H2O, 0.04mol] and 6.24g diethylenetriamine [DETA, 0.06mol] be sufficiently stirred,
Above-mentioned solution is added in the sodium hydroxide of 5.57g [NaOH, 0.14mol] later and adjusts solution ph between 8~9, stirs shape
Under state be added 26.71g silica solution (50wt%, 0.22mmol), closed strong stirring to be uniformly mixed, after being mixed thoroughly
By crystallization mixture be placed in polytetrafluoroethylene (PTFE) lining pressure vessel at 130 DEG C crystallization 7d, product washed after being filtered, washed
90 DEG C of dry 6h after washing then heat to 550 DEG C, and constant temperature calcining 6h both obtains product, are denoted as NS-3, the reactant chemistry of the system
It is as follows to measure ratio: Al2O3: SiO2: nickel amine chelate: solvent: OH-=1: 6.13: 1.25: 34.12: 1.75, table is tested through ICP
Bright Ni content and SSZ-13 molecular sieve content are listed in table 1.
[embodiment 4]
Synthesis of the nickel amine chelate as template (guiding) agent synthesizing Si-Al type CHA molecular screen material.
Weigh the sodium aluminate [NaAlO of 213.84g2, 2.61mol] and it is dissolved in the n,N-Dimethylformamide of 511.91mL
In the n,N-dimethylacetamide [DEF] of [DMF] and 357.42mL, after mixing evenly, 2.19g Ni-TETA chelate is added
(being made by nickel salt and triethylene tetramine, n (Ni:TEPA=1:1)) and 66.23g nickel chloride [NiCl2·6H2O, 0.29mol]
And 213.25g ethylenediamine [DEA, 3.54mol] is sufficiently stirred, and later adds the potassium hydroxide of 188.16g [KOH, 3.36mol]
Enter above-mentioned solution and adjust solution ph between 9~10,2653.54g white carbon black [SiO is added under stirring2, 99wt.%,
44.22mol], crystallization mixture is placed in polytetrafluoroethylene (PTFE) lining after being mixed thoroughly to being uniformly mixed by closed strong stirring
Pressure vessel at 200 DEG C crystallization 5h, product is after being filtered, washed, and 100 DEG C of dry 7h, then heat to 400 after washing
DEG C, constant temperature calcining 12h both obtains product, is denoted as NS-4, the reactant stoichiometric ratio of the system is as follows: Al2O3: SiO2: nickel amine chela
Close object: solvent: OH-=1: 16.94: 1.47: 4.25: 1.28, show Ni content and SSZ-13 molecular sieve content through ICP test
It is listed in table 1.
[embodiment 5]
Synthesis of the nickel amine chelate as template (guiding) agent synthesizing Si-Al type CHA molecular screen material.
Weigh 60.31g aluminum sulfate [[Al2(SO4)3·18H2O, purity >=98wt.%, 0.09mol] it is dissolved in 115.31mL
In deionized water and 200.36mL ethyl alcohol [EtOH], after mixing evenly, 66.23g nickel chloride [NiCl is added2·6H2O,
0.29mol] and 213.25g2,2- bipyridyl [2,2-bpy, 0.83mol] be sufficiently stirred, later by the hydroxide of 399.77g
Sodium [NaOH, 9.99mol] is added above-mentioned solution and adjusts solution ph between 11~12, and it is white that 122.15g is added under stirring
Crystallization mixture is placed in after being mixed thoroughly by carbon black (99wt%, 2.04mol), closed strong stirring to being uniformly mixed
Polytetrafluoroethylene (PTFE) lining pressure vessel at 100 DEG C crystallization 10d, product is after being filtered, washed, 100 DEG C of dry 7h after washing,
400 DEG C are then heated to, constant temperature calcining 12h both obtains product, it is denoted as NS-1, the reactant stoichiometric ratio of the system is as follows:
Al2O3: SiO2: nickel amine chelate: solvent: OH-=1: 22.67: 17.44: 209.67: 111, through ICP test show Ni content with
And SSZ-13 molecular sieve content is listed in table 1.
Table 1
[embodiment 6~20]
According to the method for embodiment 5, raw materials used sorting different ratio (table 3) is reacted in control as shown in table 2, closes respectively
At nickel amine chelate out as template (guiding) agent synthesizing Si-Al type CHA molecular screen material.
Table 2
[embodiment 21]
Ni-SSZ-13 catalyst converts the application in hydrocarbon reaction processed in methanol.
The NS-1 molecular sieve that Example 1 synthesizes carries out ammonium at 90 DEG C with 7.54wt% ammonium nitrate solution and hands over 2h.Product warp
After being filtered, washed, drying 4h at 120 DEG C, ammonium exchange of progress is repeated, after being filtered, washed, drying 4h at 120 DEG C,
Roast 4h at 600 DEG C, be made Hydrogen Ni-SSZ-13, then tabletting, break into pieces, sieve, take the particle of 20~40 mesh spare.With first
Alcohol is raw material, the fixed bed reactors for being 15 millimeters with diameter, in 430 DEG C, mass space velocity 1.5h-1, pressure be 2MPa condition
Lower examination, ethylene and propene yield achieve preferable technical effect up to 84.2%.
Table 3
[embodiment 22]
Ni-SSZ-13 catalyst converts the application in hydrocarbon reaction processed in methanol.
Catalyst is made using the method for preparing catalyst of embodiment 21, with first in the NS-2 molecular sieve that Example 2 synthesizes
Alcohol is raw material, the fixed bed reactors for being 15 millimeters with diameter, in 300 DEG C, mass space velocity 0.5h-1, pressure be 5MPa condition
Lower examination, ethylene and propene yield achieve preferable technical effect up to 80.2%.
[embodiment 23]
Ni-SSZ-13 catalyst converts the application in hydrocarbon reaction processed in methanol.
Catalyst is made using the method for preparing catalyst of embodiment 21, with first in the NS-3 molecular sieve that Example 3 synthesizes
Alcohol is raw material, the fixed bed reactors for being 15 millimeters with diameter, in 550 DEG C, mass space velocity 5.0h-1, pressure be 0.2MPa item
It is checked and rated under part, ethylene and propene yield achieve preferable technical effect up to 82.9%.
[embodiment 24]
Ni-SSZ-13 catalyst converts the application in hydrocarbon reaction processed in methanol.
Catalyst is made using the method for preparing catalyst of embodiment 21, with first in the NS-4 molecular sieve that Example 4 synthesizes
Alcohol is raw material, the fixed bed reactors for being 15 millimeters with diameter, in 490 DEG C, mass space velocity 0.75h-1, pressure be 2.25MPa
Under the conditions of check and rate, ethylene and propene yield achieve preferable technical effect up to 85.8%.
[embodiment 25]
Ni-SSZ-13 catalyst converts the application in hydrocarbon reaction processed in methanol.
Catalyst is made using the method for preparing catalyst of embodiment 21, with first in the NS-5 molecular sieve that Example 5 synthesizes
Alcohol is raw material, the fixed bed reactors for being 15 millimeters with diameter, in 600 DEG C, mass space velocity 0.3h-1, pressure be 15MPa condition
Lower examination, ethylene and propene yield achieve preferable technical effect up to 81.7%.
[comparative example 1]
Take SiO2/Al2O3The ZSM-5 molecular sieve that molar ratio is 40 is made using the method for preparing catalyst of embodiment 21 and is urged
Agent is checked and rated in the way of embodiment 24, and reaction condition evaluates ethylene and propene yield up to 32.7%.
[comparative example 2]
Take SiO2/Al2O3The SAPO-34 molecular sieve that molar ratio is 6.7, using the method for preparing catalyst system of embodiment 21
Catalyst is obtained, is checked and rated in the way of embodiment 24, reaction condition evaluates ethylene and propene yield up to 74.1%.
[comparative example 3]
Take SiO2/Al2O3The Cu-SSZ-13 molecular sieve that molar ratio is 30, using the method for preparing catalyst system of embodiment 21
Catalyst is obtained, is checked and rated in the way of embodiment 24, reaction condition evaluates ethylene and propene yield up to 68.7%.
[embodiment 26]
Application of the Ni-SSZ-13 catalyst in hydrogenation reaction.
The NS-7 molecular sieve that Example 7 synthesizes is made catalyst using the method for preparing catalyst of embodiment 21, will urge
Agent restores 12h at 500 DEG C in 1.5L/min flow of pure hydrogen, obtains metal mold Ni-SSZ-13 catalyst.Due to cracking
Aromatic hydrocarbons accounts for 65~80% in carbon nine and its above hydrocarbon-fraction, simultaneously containing a large amount of polymerizable unsaturated components, the choosing of this test example
With carbon nine and its above hydrocarbon and saturated hydrogenation oil raw material (specific component is shown in Table 4) obtained according to a certain ratio is cracked, this is carried out
The test of invention catalyst hydrogenation activity.Process conditions are as follows: 60 DEG C of inlet temperature, pressure 2.5MPa, green oil air speed LHSV=
2.0h-1, hydrogen to oil volume ratio H2/ feedstock oil=550:1, experimental result are shown in Table 5.
Table 4
[comparative example 4]
Take Ni/Al2O3-SiO2Catalyst carries out hydrogenation activity test according to the condition of embodiment 26, as a result such as table 5.
Table 5
[embodiment 27]
Application of the Ni-SSZ-13 in olefin cracking reaction.
The NS-16 molecular sieve that embodiment 16 synthesizes is chosen, catalyst is made using the method for preparing catalyst of embodiment 21,
Reaction temperature be 650 DEG C, reaction pressure 0.02MPa, weight space velocity 1h-1Under conditions of check and rate, the results are shown in Table 6.
[comparative example 5]
Take SiO2/Al2O3Catalysis is made using the method for preparing catalyst of embodiment 21 in the modenite that molar ratio is 12
Agent is checked and rated in the way of embodiment 27, as a result such as table 6.
[comparative example 6]
Take SiO2/Al2O3Catalyst is made using the method for preparing catalyst of embodiment 21 in the β zeolite that molar ratio is 37,
It is checked and rated in the way of embodiment 27, as a result such as table 6.
[comparative example 7]
Take SiO2/Al2O3Catalyst is made using the method for preparing catalyst of embodiment 21 in the Y zeolite that molar ratio is 16,
It is checked and rated in the way of embodiment 27, as a result such as table 6.
[comparative example 8]
Take SiO2/Al2O3The ZSM-5 molecular sieve that molar ratio is 39 is made using the method for preparing catalyst of embodiment 21 and is urged
Agent is checked and rated in the way of embodiment 27, as a result such as table 6.
Table 6
Claims (9)
1. a kind of Ni-SSZ-13 catalyst, based on parts by weight, including following components:
(1) 0.1~20 part of Ni or its oxide；
(2) 80~99.9 parts of SSZ-13 molecular sieve；The preparation method of the catalyst comprises the following steps:
A, with raw materials used molar ratio Al2O3: SiO2: nickel amine chelate: solvent: OH-For 1: 1~500: 1~500: 10~
1000: 1~100, silicon source and solvent are sufficiently stirring and mixing to form solution A first；
B, nickel salt, chelating agent and/or nickel amine chelate are added in solution A and are sufficiently stirred, and be added in whipping process inorganic
Alkali regulation system pH value forms solution A between 7~121；
C, A is added in silicon source needed for reaction1Uniform crystallization mixture A is formed after being sufficiently stirred in solution2；
D, by crystallization mixture A2Crystallization 5h~10 day obtain crystallization product at a temperature of 100~200 DEG C；
E, final products will be obtained after crystallization product washing, drying and roasting；
Wherein, the nickel source of the nickel amine chelate is selected from one of the sulfate of nickel, nitrate, carbonate, acetate；Chelating
Agent is selected from ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, 1,10- Phen, 2,2- bipyridyl or 4,4-
At least one of bipyridyl.
2. Ni-SSZ-13 catalyst according to claim 1, it is characterised in that based on parts by weight, Ni or its oxide
Content be 0.5~18 part.
3. Ni-SSZ-13 catalyst according to claim 1, it is characterised in that catalyst passes through fabricated in situ.
4. Ni-SSZ-13 catalyst according to claim 1, it is characterised in that raw materials used molar ratio Al2O3:
SiO2: nickel amine chelate: solvent: OH-It is 1: 3~300: 2~200: 30~600: 2~80.
5. Ni-SSZ-13 catalyst according to claim 4, it is characterised in that raw materials used molar ratio Al2O3:
SiO2: nickel amine chelate: solvent: OH-It is 1: 5~200: 5~120: 100~400: 5~50.
6. Ni-SSZ-13 catalyst according to claim 5, it is characterised in that raw materials used molar ratio Al2O3:
SiO2: nickel amine chelate: solvent: OH-It is 1: 10~100: 10~60: 150~300: 8~40.
7. application of any one of the claim 1~6 Ni-SSZ-13 catalyst in methanol hydrocarbon reaction.
8. any one of the claim 1~6 Ni-SSZ-13 catalyst is in unsaturated compound or with the high score of unsaturated bond
Application in the hydrogenation of son.
9. application of any one of the claim 1~6 Ni-SSZ-13 catalyst in hydrocarbon cracking reaction.
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| CN101273000A (en) * | 2005-08-08 | 2008-09-24 | 切夫里昂美国公司 | Catalyst and process for selective hydroconversion of normal paraffing to normal paraffin-rich lighter products |
| JP2012523958A (en) * | 2009-04-17 | 2012-10-11 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニー | Small pore molecular sieve supported copper catalyst for the reduction of nitrogen oxides with durability against lean / rich aging |
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| CN101273000A (en) * | 2005-08-08 | 2008-09-24 | 切夫里昂美国公司 | Catalyst and process for selective hydroconversion of normal paraffing to normal paraffin-rich lighter products |
| JP2012523958A (en) * | 2009-04-17 | 2012-10-11 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニー | Small pore molecular sieve supported copper catalyst for the reduction of nitrogen oxides with durability against lean / rich aging |
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