CN104289251B - Non-precious metal catalyst for hydrocarbon isomerization and preparation method and application - Google Patents
Non-precious metal catalyst for hydrocarbon isomerization and preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of non-precious metal catalyst for hydrocarbon isomerization and preparation method and application.Described hydrocarbon isomerization non-precious metal catalyst is to be prepared from, wherein with the supported carrier base metal active component that SAPO 11 system with molecular sieve for preparing is standby: SAPO 11 molecular sieve external surface area 200 280m2/ g, middle strong acid acid amount 120 200 μm ol/g；Base metal active component is selected from two kinds in Ni, Mo, W, Co, active component content 5～20wt% in catalyst.Present invention also offers the application in the double branched chain isomerization reaction of catalysis hydrocarbon isomerization particularly hydro carbons of the described non-precious metal catalyst.Non-precious metal catalyst prepared by the present invention not only has hydrocarbon isomerization the most double branched chain isomer performance of excellence, and has good sulfur resistance and activity stability.
Description
Technical field
The present invention relates to a kind of non-precious metal catalyst for hydrocarbon isomerization and preparation method and application, specifically
Relate to the base metal catalysis that a kind of SAPO-11 molecular sieve to have bigger external surface area and relatively peracidity is prepared for carrier
Agent, the preparation method of this catalyst and utilize this catalyst to carry out the double branched chain isomerization reaction of hydrocarbon isomerization particularly hydro carbons
Method.
Background technology
Hydrocarbon isomerization is one of most important catalytic conversion process in petrochemical industry, can be applicable to improve gasoline
Octane number, reduce all many-sides such as diesel-fuel pour point and the viscosity temperature characteristic improving lube base oil.In recent years, to oil of high quality
Being continuously increased so that the research and development of hydrocarbon isomerization technology are increasingly paid close attention to by people of product demand.Only with high-quality
As a example by the production of motor petrol, highly-branched chain isomerous alkane is the optimal blend component in high-quality cleaning motor petrol, makes gasoline
In alkene or full close after n-alkane to be converted into the isoparaffin of double side chain or highly branched chain be to improve octane number
Good means, exploitation has highly active hydro carbons isomery the most double branched chain isomer catalyst to cleaning and ultra-clean motor petrol
Production tool be of great significance.
Currently, the hydrocarbon isomerization catalyst of industrial employing is bifunctional catalyst, i.e. by having acid function
Molecular sieve and the metal two parts with hydrogenation-dehydrogenation function are constituted, as by United States Patent (USP) USP5057471 and USP8198501
Disclosed hydrocarbon isomerization catalyst.Although these catalyst have advantage clearly, but it is tight to there is also cracking reaction
The shortcomings such as weight, double branched chain isomer selectivitys are low.Therefore, need the hydrocarbon isomerization catalyst that exploitation is novel badly, especially possess
The catalyst of the double branched chain isomer function of hydro carbons.
Silicon phosphate aluminium profiles (SAPO) molecular sieve is that U.S. combinating carbide company is in a novel non-boiling of class of invention in 1984
Stone-type molecular sieve, receives extensively attention in catalytic field.SAPO-n is to be replaced AlPO by Si atom4P in-n skeleton or
After Al atom formed by AlO4、PO4And SiO4The non-neutral framework of molecular sieve that tetrahedron is constituted.SAPO-11 molecular sieve conduct
A member in SAPO-n type molecular sieves, is the molecular sieve for hydrocarbon isomerization of most study in recent ten years, and it is special
The hydrocarbon isomerization performance of the acid catalyst excellence given with it as carrier of different pore passage structure and gentleness.
Research currently for SAPO-11 molecular sieve based catalyst is devoted to improve the catalyst isomerization to hydro carbons more
Selectivity, and do not focus on high-octane pair of branched chain isomer alkane of fecund, as (open in Chinese patent application 02136301.3
Number CN1392099A).Therefore, if these SAPO-11 molecular sieves are applied to improve the process of octane number, generated is different
Structure product is single branched chain isomer that octane number is the highest, and the higher double branched chain isomer yield of octane number are less.Remove
Outside this, SAPO-11 molecular sieve coordinates precious metals pt to use mostly, and noble metal is not appropriate for for sour product, and cost
The highest.It would therefore be highly desirable to exploitation had not only had the double branched chain isomer function of hydro carbons of excellence, and but also had had the SAPO-11 of resistance to sulfur functional and divide
Son sieve base catalyst.
Summary of the invention
It is an object of the present invention to, for the problem existing for hydrocarbon isomerization catalyst in above-mentioned prior art, carry
Urge having bigger external surface area and the base metal prepared compared with the novel SAPO-11 molecular sieve of peracidity for carrier for a kind of
Agent, to overcome the shortcoming that current hydrocarbon isomerization noble metal catalyst cost is high, sulfur tolerance is poor.
Another object of the present invention is to provide the preparation method of described non-precious metal catalyst.
Another object of the present invention is to provide described non-precious metal catalyst answering in catalysis hydro carbons isomerization reaction
With.
Another object of the present invention is to provide a kind of hydrocarbon isomerization method applying described non-precious metal catalyst.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of hydrocarbon isomerization non-precious metal catalyst, this catalyst
It is to be prepared from, wherein with the supported carrier base metal active component that SAPO-11 system with molecular sieve for preparing is standby:
Described SAPO-11 molecular sieve external surface area 200-280m2/ g, in strongAcid acid amount 120-200 μm ol/
g；
Described base metal active component is selected from two kinds in Ni, Mo, W, Co, on the basis of the gross weight of catalyst, with
The oxide meter of activity component metal, in catalyst in the active component content 5～20wt%(present invention, in addition to indicating especially, institute
State content and be weight content and ratio with ratio).
According to the preferred embodiment of the present invention, in the catalyst of the present invention, described base metal active component is
One of Ni-Mo, Ni-W or Ni-Co combination.In terms of the oxide of activity component metal, the content of metal active constituent Ni is 3-
6%, Mo, the content of W or Co are 5-8%.
According to double-function catalyzing reaction mechanism, the association between acid function and the hydrogenation-dehydrogenation function of metal of molecular sieve
It it is the key obtaining excellent hydrocarbon isomerization catalyst with coupling.Inventor has carried out substantial amounts of research to this, finally carries
Go out the catalyst of the present invention.
Double branched chain isomers of hydro carbons are owing to having bigger volume, and it can only be looked unfamiliar in the appearance of SAPO-11 molecular sieve
Becoming, and the conventional SAPO-11 molecular sieve of prior art is relatively big due to crystallite dimension, external surface area is the least, is available for double branched chain isomer
The place that body generates is limited, thus only has fairly limited double branched chain isomerization activity.Meanwhile, more weak for SAPO-11 acidity
Also the generation of double branched chain isomer it is unfavorable for.
According to specific embodiments of the present invention, SAPO-11 molecular sieve used by the present invention has with conventional SAPO-11 molecular sieve
Different characterisitic parameters, its external surface area 200-280m2/ g, in strongAcid acid amount 120-200 μm ol/g.For making
SAPO-11 molecular sieve has bigger external surface area, relatively peracidity to meet the needs of the present invention, and SAPO-11 is divided by the present invention
The synthetic method of son sieve is improved.Specifically, there is bigger external surface area, relatively peracidity described in the present invention
SAPO-11 molecular sieve is to use two sections of crystallization method synthesis, and its concrete preparation process includes:
(1) by phosphorus source, aluminum source, water, di-n-propylamine and Organic Alcohol by (0.5-2.5): 1:(20-50): (0.7-2.0):
(0.1-50) mol ratio (based on oxide) mixes mutually, after stirring, carries out crystallization 3-8h in 130-180 DEG C, is formed
Precursor sol；
(2) in precursor sol, add cationic surfactant, organosilicon source, or add suitable quantity of water, warp further
Stirring, aging after at 160-200 DEG C crystallization 20-40h；
(3) solid product separated, wash, be dried and roasting 4-8 hour under the air atmosphere of 400-650 DEG C, obtain
SAPO-11 molecular sieve.
According to the preferred embodiment of the present invention, during above-mentioned preparation SAPO-11 molecular sieve, described cation
Surfactant is Dodecyl trimethyl ammonium chloride (DoTAB).Preferably, the addition of this cationic surfactant is it
It is (0.001-0.003) with the mol ratio in aluminum source in system: 1.
According to specific embodiments of the present invention, the preparation method of the described SAPO-11 molecular sieve of the present invention, at second segment
During crystallization (above-mentioned steps (2)), preferably organosilicon source described in controlling crystallizing system: aluminum source: phosphorus source: di-n-propylamine: have
Machine alcohol: surfactant (DoTAB): the mol ratio of water is (0.1-2.0): 1:(0.5-2.5): (0.7-2.0): (0.1-
50): (0.001-0.003): (20-60).
In the preparation method of the described SAPO-11 molecular sieve of the present invention, mole joining of described organosilicon source, aluminum source and phosphorus source
Ratio is respectively with SiO2、Al2O3And P2O5Meter.
According to specific embodiments of the present invention, in the preparation process of the described SAPO-11 molecular sieve of the present invention, raw material
In the selection in phosphorus source, aluminum source and organosilicon source can be raw material commonly used in prior art, the present invention limits the most especially
System.Such as, phosphorus source can be phosphoric acid, phosphorous acid, and aluminum source can be boehmite, aluminum isopropylate., and organosilicon source just can be
Silester, positive silicic acid propyl ester etc..In the preparation process of the described SAPO-11 molecular sieve of the present invention, wherein said Organic Alcohol with
The alcohol that the hydrolysis of described organosilicon source generates is identical.
According to the preferred embodiment of the present invention, of the present invention have bigger external surface area, relatively peracidity
SAPO-11 molecular sieve prepares in accordance with the following methods:
(1) by phosphorus source, aluminum source and water by certain mol ratio mixing, and stirring is equal in the water bath with thermostatic control of 30～40 DEG C
Even；Add di-n-propylamine and Organic Alcohol, after mixing and stirring, load the rustless steel reaction under high pressure that liner is politef
In still, under the self-generated pressure of 130～180 DEG C, hydrothermal crystallizing 3～8h forms precursor sol；Phosphorus source in wherein, control system,
The mol ratio of aluminum source, water, di-n-propylamine and Organic Alcohol is (0.5-2.5): 1:(20-50): (0.7-2.0): (0.1-50)；
(2) in the precursor sol be cooled to room temperature, quantitative cationic surfactant, organosilicon source and water is added,
Continue to stir until forming uniform gel, and at 55～65 DEG C, stand aging 10-34h, afterwards, this gel is loaded stainless
In steel autoclave, under the self-generated pressure of 185-200 DEG C, hydrothermal crystallizing 20-30h, obtains solid product；Wherein, control volume
In system, organosilicon source, aluminum source, phosphorus source, di-n-propylamine, Organic Alcohol, surfactant (DoTAB), the mol ratio of water are (0.1-
2.0): 1:(0.5-2.5): (0.7-2.0): (0.1-50): (0.001-0.003): (20-60)；
(3) being taken out by the solid product obtained, cooled, centrifugation is also washed to neutral, puts into baking oven at 120 DEG C
Temperature is dried, and high-temperature roasting 5-8h in the Muffle furnace of 500-650 DEG C, obtains SAPO-11 zeolite product.
In the skeleton forming process of SAPO-11, first phosphorus aluminum combine the electroneutral AlPO of formation4-11 skeletons, afterwards silicon
Enter skeleton in two ways: 1 Si replaces a P；2 Si replace 1 Al and 1 P, make original electroneutral molecular sieve
There is tradable electric charge, formed acidic site.According to specific embodiments of the present invention, in the synthesis of SAPO-11 molecular sieve,
Use the surface that two sections of crystallization and the rear mode introducing silicon source can make more Si atom be distributed in SAPO-11 molecular sieve, from
And produce more acidic site contacted, strong in making in prepared SAPO-11 molecular sieveAcid acid amount is 120-200
μm ol/g, this value is strong in being far longer than in the SAPO-11 molecular sieve prepared by prior artAcid acid value；And it is positive
The introducing of ionic surface active agent then can play peptizaiton, and the multiple cationic surfactant of inventor's investigation and comparison
Peptizaiton, find wherein with main chain with the cationic surfactant of 12 carbon atoms, the most of the present invention
Dodecyl trimethyl ammonium chloride is maximum to the peptizaiton of SAPO-11 molecular sieve precursor crystallite, and this greatly reduces SAPO-
The crystallite dimension of 11 molecular sieves, so that the external surface area of SAPO-11 molecular sieve can increase to 200-280m2/ g is the biggest.
According to specific embodiments of the present invention, in order to avoid metal active constituent is poisoned by impurity such as S, N, As, this
Invention uses base metal as hydrogenation-dehydrogenation active component.Single for metal component, the premise of selection possesses enough
Hydrogenation-dehydrogenation performance.The catalysis activity of metal is closely related with the d track of its atom, generally uses d percent (d%) to come quantitatively
D electronic state in statement metallic atom.D% is the biggest, and the electronics that in corresponding metallic atom, d can carry is filled the most, then d electronics
Hole is the fewest, and the degree of d electron hole is the key of absorption and the catalytic performance affecting metal.Absorbability may be led the most by force
Cause Irreversible Adsorption, and the most weak activated reactant molecule that is not enough to of absorbability, it is therefore desirable to the absorbability of metal is moderate.Right
For hydrogenation catalyst, d%=40～50% is optimal.In the current various base metal active components having obtained commercial Application
In, the d%=40% of the d%=43% of the d%=43% of the d%=40% of Ni, Mo, W, Co.Therefore, in the preparation process in accordance with the present invention, use
Two of which in these several base metals.
The supported carrier base metal active component standby with SAPO-11 system with molecular sieve for preparing of the present invention and the catalyst that is prepared as
Can be described as SAPO-11 molecular screen base non-precious metal catalyst, it can use as hydrocarbon isomerization catalyst, is possible not only to overcome
The shortcoming that noble metal catalyst cost is high at present, sulfur tolerance is poor, it is also possible to obtain higher double branched chain isomer selectivitys.
On the other hand, present invention also offers the preparation method of described SAPO-11 molecular screen base non-precious metal catalyst, should
Method includes step:
(1) by described SAPO-11 molecular sieve, boehmite and sesbania powder mix homogeneously and grind, peptization is added afterwards
Agent dilute nitric acid solution, extruded moulding is also dried, obtains solid carrier；
(2) preparation Ni and Mo, the impregnation liquid of W or Co, uses equi-volume impregnating by base metal active component (such as
Ni-Mo, Ni-W or Ni-Co) impregnated on the solid carrier being dried；
(3) be dried by the solid product obtained after dipping non-noble metal components, roasting i.e. can get use of the present invention
Catalyst in the double branched chain isomer of hydro carbons.
In the preparation method of the above-mentioned SAPO-11 molecular screen base non-precious metal catalyst of the present invention, intend described in step (1)
Boehmite and sesbania powder use the conventional amount used of art respectively as binding agent and extrusion aid, its consumption, this
It is 50～80wt%(finally prepared for preferably controlling the amount of SAPO-11 molecular sieve in final preparation-obtained catalyst in bright
To catalyst in, in addition to the oxide and SAPO-11 molecular sieve of described base metal active component, remaining mainly bonding
Agent).
In the preparation method of the above-mentioned SAPO-11 molecular screen base non-precious metal catalyst of the present invention, the leaching of Ni, Mo, W and Co
Stain liquid can be respectively adopted Ni (NO3)2、(NH4)6MoO24、(NH4)6H2W12O40With Co (NO3)2Solution.Incipient impregnation is preferably
In the way of co-impregnation, two kinds of active components be impregnated on carrier simultaneously.
In the preparation method of the SAPO-11 molecular screen base non-precious metal catalyst of the present invention, the concrete behaviour mentioned the most in detail
Make (to include that the acid in carrier preparation process is molten, extruded moulding, be dried, and impregnated being dried of catalyst of active component, roasting
The processes such as burning) can use the routine operation of art, such as, described being dried can be place 4～14h at normal temperatures after,
2～6h it are dried at 80～140 DEG C；Described roasting condition is usually roasting 2～6h at 400～800 DEG C.
On the other hand, present invention also offers described SAPO-11 molecular screen base non-precious metal catalyst at catalysis hydro carbons
Application in the double branched chain isomerization reaction of isomerization particularly hydro carbons.The double branched chain isomerization reaction of described hydro carbons can be such as
Double branched chain isomerization reaction of normal octane；Double branched chain isomerization reaction of normal heptane；Double branched chain isomerization of positive octene react and
Comprise double branched chain isomerization reaction of the true gasoline of various straight chain hydrocarbon.
On the other hand, present invention also offers a kind of hydrocarbon isomerization method applying described non-precious metal catalyst.Should
Method mainly uses the non-precious metal catalyst of the present invention as the double branched chain isomerization reaction of hydrocarbon isomerization particularly hydro carbons
Catalyst.When being embodied as, preferably controlling isomerization reaction condition in the present invention is: reaction pressure 1-2MPa, weight (hourly) space velocity (WHSV)
(WHSV)1.5-3.5h-1, reaction temperature 593-723K, hydrogen-oil ratio (n (H2)/n (oil)) 300-500.Catalyst needs before the reaction
Processing through presulfurization, sulfurized oil is containing 3wt%CS2Normal octane solution.Conditions of vulcanization is: pressure (P)=2.8MPa, weighs space-time
Speed (WHSV)=2.0h-1, temperature (T)=613K, hydrogen-oil ratio [n (H2)/n(oil)]=300.Treat that catalyst pretreatment process completes
After, device is transferred to P=1-2MPa, WHSV=1.5-3.5h-1, T=593-723K, n (H2The isomerization of)/n (oil)=300-500
Reaction condition, opens injection valve, pumps into raw material and reacts, and generally charging 3h reaction is the most stable.
Compared with prior art gained hydrocarbon isomerization catalyst, non-precious metal catalyst provided by the present invention is utilized to enter
Row hydrocarbon isomerization, is possible not only to overcome the shortcoming that current noble metal catalyst cost is high, sulfur tolerance is poor, it is also possible to obtain relatively
High double branched chain isomer selectivitys.
Accompanying drawing explanation
Fig. 1 is the NiMo/SAPO-11-T-D catalyst of the embodiment of the present invention 1 preparation, the NiW/SAPO-of embodiment 2 preparation
11-T-D catalyst and the X ray diffracting spectrum of conventional SAPO-11 molecular sieve.
Detailed description of the invention
Realization and the feature of technical solution of the present invention are discussed in detail, to help to understand the present invention below in conjunction with specific embodiment
Spirit and beneficial effect, but can not constitute can any restriction of practical range to the present invention.
(T represents two sections of crystallization method synthesis, and D represents cation form in the synthesis of embodiment 1NiMo/SAPO-11-T-D catalyst
Face activating agent DoTAB)
First, two sections of crystallization method synthesis SAPO-11 molecular sieves are used: weigh 13.6g phosphoric acid, 9.0g boehmite (contains
70.3%Al2O3) and 30.0g deionized water, stir in the water bath with thermostatic control of 35 DEG C；It is slowly added to the most successively
7.6g di-n-propylamine and 11.3g propanol；The rustless steel autoclave that liner is politef is loaded after mixing and stirring
In, under the self-generated pressure of 160 DEG C, hydrothermal crystallizing 6h forms precursor sol；0.06g is added in the colloidal sol be cooled to room temperature
DoTAB, 5.0g positive silicic acid propyl ester and 10.0g water, continue to stir until forming uniform gel, and stand aging at 60 DEG C
24h, afterwards, loads this gel in rustless steel autoclave, hydrothermal crystallizing 24h under the self-generated pressure of 185 DEG C, consolidate
Body product；Finally being taken out by the solid product obtained, cooled, centrifugation is also washed to neutral, puts into baking oven in 120 DEG C of bakings
Dry, obtain SAPO-11 molecular screen primary powder；By SAPO-11 molecular screen primary powder high-temperature roasting 6h in the Muffle furnace of 600 DEG C, to obtain final product
External surface area is 241m2/ g, in strongAcid acid amount is the SAPO-11-T-D molecular sieve of 153.6 μm ol/g.
By SAPO-11-T-D molecular sieve, boehmite and sesbania powder mix homogeneously and grind, add appropriate dilute afterwards
Salpeter solution, through extruded moulding, is dried etc. after program, impregnating metal component.The dipping of metal component uses incipient impregnation
Method, impregnation liquid is Ni (NO3)2(NH4)6MoO24Mixed solution, based on oxide, pickup is respectively Ni4wt%,
Mo6wt%.NiMo/SAPO-11-T-D catalyst is i.e. obtained through programs such as dry, roastings after dipping.The X-ray diffraction of this catalyst
Collection of illustrative plates is as shown in Figure 1.
(C represents conventional crystallization method synthesis, and D represents cation form in the synthesis of comparative example 1NiMo/SAPO-11-C-D catalyst
Face activating agent DoTAB)
First, one section of conventional crystallization method synthesis SAPO-11 molecular sieve is used: by 40.0g deionized water and 13.6g phosphoric acid
It is mixed to form colloidal sol in 35 DEG C of water-baths；Add 9.0g boehmite, stir 90min, add 5.0g positive silicic acid propyl ester and
0.06g DoTAB, continues stirring 120min, is slow added into template di-n-propylamine 7.6g, continue stirring, until being formed uniformly
Initial gel mixture；Above-mentioned initial gel mixture is loaded with in teflon-lined stainless steel cauldron,
Crystallization 24h at 185 DEG C, obtains solid product；By solid product separate, washing, 120 DEG C be dried, roasting 6h at 600 DEG C,
To SAPO-11 molecular sieve.
Afterwards, by SAPO-11 molecular sieve, boehmite and sesbania powder mix homogeneously and grind, add appropriate dilute nitre
Acid solution, through extruded moulding, is dried etc. after program, impregnating metal component.The dipping of metal component uses the side of incipient impregnation
Method, impregnation liquid is Ni (NO3)2(NH4)6MoO24Mixed solution, based on oxide, pickup is respectively Ni4wt%,
Mo6wt%.NiMo/SAPO-11-C-D catalyst is i.e. obtained through programs such as dry, roastings after dipping.
The pore structure data of catalyst prepared in embodiment 1 and comparative example 1 are as shown in table 1, and acid characterization result is such as
Shown in table 2.
The pore structure parameter of the catalyst in table 1 embodiment 1 and comparative example 1
As seen from Table 1, compared with conventional hydrothermal synthetic method, under the auxiliary of DoTAB, use synthesized by two sections of crystallization methods
SAPO-11 base catalyst have bigger external surface area and mesoporous pore volume, this is attributable under two sections of crystal patterns,
The dispersibility of DoTAB makes prepared SAPO-11 molecular sieve have a less crystallite dimension, and the external surface area being significantly increased
Just it is being derived from the reduction of zeolite crystal size.
The acid amount (calculating according to pyridine-Infrared Characterization result) of the catalyst in table 2 embodiment 1 and comparative example 1
As seen from Table 2, compared with conventional hydrothermal synthetic method, the SAPO-11 base catalyst synthesized by two sections of crystallization methods has
More can be used in isomerization strongAcid position.
With n-C8For model compound, investigate the isomerization reaction performance of obtained SAPO-11 base catalyst, evaluated
Carrying out in fixed bed reactors continuously, the loadings of catalyst is 3g.Catalyst needs to process through presulfurization before evaluation, sulfuration
Oil is containing 3wt%CS2Normal octane solution.Conditions of vulcanization is: pressure (P)=2.8MPa, weight (hourly) space velocity (WHSV) (WHSV)=2.0h-1, temperature
(T)=613K, hydrogen-oil ratio [n (H2)/n(oil)]=300.After catalyst pretreatment process completes, device is transferred to following commenting
Covalent reaction condition: reaction pressure 1.5MPa, reaction temperature 340 DEG C, hydrogen alkane volume ratio 400:1, weight (hourly) space velocity (WHSV) 1.5h-1, open into
Sample valve, pumps into raw material and reacts, and after charging 3h stable reaction, collects condensed fluid product, uses chromatography to carry out product
Analyze.Evaluation result is shown in Table 3.
N-C on catalyst in table 3 embodiment 1 and comparative example 18Isomerization reaction result
| NiMo/SAPO-11-T-D | NiMo/SAPO-11-C-D | |
| Conversion ratio (%) | 83.6 | 81.9 |
| Single branched chain isomer C8Selectivity (%) | 65.6 | 74.7 |
| Double branched chain isomers C8 selectivity (%) | 32.1 | 6.7 |
| Cracking Selectivity (%) | 1.8 | 13.6 |
To compare n-C8Isomerization reaction result can find, with the NiMo/SAPO-prepared by the method for present invention offer
11-T-D catalyst, compared with NiMo/SAPO-11-C-D catalyst prepared by conventional method, has higher pair of branched chain isomer
Body selectivity and lower Cracking Selectivity, this is strong in having more owing to the catalyst prepared by the present inventionAcid
Position and bigger external surface area.
Embodiment 2, (T represents the synthesis of two sections of crystallization methods, and D represents cation in the synthesis of NiCo/SAPO-11-T-D catalyst
Surfactant D oTAB)
First, two sections of crystallization method synthesis SAPO-11 molecular sieves are used: weigh 15.2g phosphoric acid, 9.0g boehmite (contains
70.3%Al2O3) and 47.0g deionized water, stir in the water bath with thermostatic control of 35 DEG C；It is slowly added to the most successively
4.6g di-n-propylamine and 2.9g propanol；The rustless steel autoclave that liner is politef is loaded after mixing and stirring
In, under the self-generated pressure of 160 DEG C, hydrothermal crystallizing 6h forms precursor sol；0.02g is added in the colloidal sol be cooled to room temperature
DoTAB, 13.8g positive silicic acid propyl ester and 10.0g water, continue to stir until forming uniform gel, and stand aging at 60 DEG C
24h, afterwards, loads this gel in rustless steel autoclave, hydrothermal crystallizing 24h under the self-generated pressure of 185 DEG C, consolidate
Body product；Finally being taken out by the solid product obtained, cooled, centrifugation is also washed to neutral, puts into baking oven in 120 DEG C of bakings
Dry, obtain SAPO-11 molecular screen primary powder；By SAPO-11 molecular screen primary powder high-temperature roasting 6h in the Muffle furnace of 600 DEG C, to obtain final product
External surface area is 252m2/ g, in strongAcid acid amount is the SAPO-11-T-D molecular sieve of 159.3 μm ol/g.
Afterwards, by SAPO-11-T-D molecular sieve, boehmite, sesbania powder and dilute nitric acid solution mix homogeneously, through extrusion
Molding, it is dried etc. after program, impregnating metal component.Impregnation liquid is Ni (NO3)2With Co (NO3)2Mixed solution, by oxide
Meter, pickup is respectively Ni3wt%, Co10wt%.NiCo/SAPO-11-T-D catalysis is i.e. obtained through programs such as dry, roastings after dipping
Agent.
Comparative example 2-1, NiCo/SAPO-11-T-C catalyst synthesis (T represents the synthesis of two sections of crystallization methods, C represents positive from
Sub-surface activating agent CTAB)
In example 2, simply cationic surfactant DoTAB is changed into cetyl trimethylammonium bromide
(CTAB), remaining component and operation are constant, prepare NiCo/SAPO-11-T-C catalyst.
Comparative example 2-2, the synthesis (T represents two sections of crystallization method synthesis) of NiCo/SAPO-11-T catalyst
First preparing SAPO-11-T molecular sieve, concrete preparation method is same as in Example 2, simply in the synthesis of molecular sieve
In do not introduce cationic surfactant DoTAB.Afterwards, NiCo/SAPO-is prepared through preparation procedure similarly to Example 2
11-T catalyst.
The pore structure data of catalyst prepared in embodiment 2 and comparative example 2-1, comparative example 2-2 are as shown in table 4, acid
Property characterization result is as shown in table 5.
The pore structure parameter of the catalyst in table 4 embodiment 2 and comparative example 2-1, comparative example 2-2
As seen from Table 4, compared with not introducing cationic surfactant, under cationic surfactant assists, adopt
Having bigger external surface area and mesoporous pore volume with the SAPO-11 base catalyst synthesized by two sections of crystallization methods, this is attributable to
The peptizaiton of cationic surfactant, makes prepared SAPO-11 molecular sieve have less crystallite dimension, and increases
External surface area is just being derived from the reduction of zeolite crystal size.Meanwhile, compared with CTAB, the dispersibility of DoTAB is more
By force, the external surface area making obtained SAPO-11 molecular sieve is maximum, brings unforeseeable significant technique effect.
The acid amount of the catalyst in table 5 embodiment 2 and comparative example 2-1, comparative example 2-2 is (according to pyridine-Infrared Characterization result
Calculate)
As seen from Table 5, there is the SAPO-11 base catalyst of maximum external surface area have and more can be used for isomerization
In strongAcid position.
With n-C8For model compound, investigate the isomerization reaction performance of obtained SAPO-11 base catalyst, evaluated
Carrying out in fixed bed reactors continuously, the loadings of catalyst is 3g.Catalyst needs to process through presulfurization before evaluation, sulfuration
Oil is containing 3wt%CS2Normal octane solution.Conditions of vulcanization is: pressure (P)=2.8MPa, weight (hourly) space velocity (WHSV) (WHSV)=2.0h-1, temperature
(T)=613K, hydrogen-oil ratio [n (H2)/n(oil)]=300.After catalyst pretreatment process completes, device is transferred to following commenting
Covalent reaction condition: reaction pressure 1.5MPa, reaction temperature 400 DEG C, hydrogen alkane volume ratio 350:1, weight (hourly) space velocity (WHSV) 1.5h-1, open into
Sample valve, pumps into raw material and reacts, and after charging 3h stable reaction, collects condensed fluid product, uses chromatography to carry out product
Analyze.Evaluation result is shown in Table 6.
N-C on catalyst in table 6 embodiment 2 and comparative example 2-1, comparative example 2-28Isomerization reaction result
Relatively n-C8Isomerization reaction result can find, with the present invention provide method prepared by there is bigger outer surface
Long-pending and more polyoxybiontic NiCo/SAPO-11-T catalyst, has higher pair of branched chain isomer selectivity and lower cracking choosing
Selecting property.
Embodiment 3, the synthesis of NiW/SAPO-11-T-D catalyst
First, two sections of crystallization method synthesis SAPO-11-T-D molecular sieves, concrete preparation method and phase described in embodiment 1 are used
With.Afterwards, by SAPO-11 molecular sieve, boehmite, sesbania powder and dilute nitric acid solution mix homogeneously, through extruded moulding, it is dried
After program, impregnating metal component.Impregnation liquid is Ni (NO3)2(NH4)6H2W12O40Mixed solution, based on oxide, dipping
Amount is respectively Ni3.5wt%, W7wt%.NiW/SAPO-11-T catalyst is i.e. obtained through programs such as dry, roastings after dipping.This catalysis
The X ray diffracting spectrum of agent is as shown in Figure 1.
Comparative example 3, the synthesis of Pt/SAPO-11-T-D catalyst
Change the impregnation liquid in embodiment 2 into H2PtCl6, based on oxide, the load capacity of Pt is 0.5wt%.Remaining operation
The most same as in Example 2, it is thus achieved that Pt/SAPO-11-T catalyst.
With true catalytically cracked gasoline as reaction raw materials, investigate the isomerization reaction of obtained SAPO-11 base catalyst
Performance, evaluates and carries out in continuous fixed bed reactors, and the loadings of catalyst is 4g.Catalyst needs through pre-sulfur before evaluation
Change processes, and sulfurized oil is containing 3wt%CS2Normal octane solution.Conditions of vulcanization is: pressure (P)=2.8MPa, weight (hourly) space velocity (WHSV) (WHSV)
=2.0h-1, temperature (T)=613K, hydrogen-oil ratio [n (H2)/n(oil)]=300.After catalyst pretreatment process completes, by device
It is transferred to following evaluation response condition: reaction pressure 1.5MPa, reaction temperature 320 DEG C, hydrogen alkane volume ratio 400:1, weight (hourly) space velocity (WHSV)
1.5h-1, open injection valve, pump into raw material and react, after charging 3h stable reaction, collect condensed fluid product, use chromatograph
Product is analyzed by method.Evaluation result is shown in Table 7.
Table 7 raw material composition and plant running 20h, 50h and 100h after reaction result
As shown in Table 7, the NiW/SAPO-11-T-D catalyst prepared by embodiment 3 after having run 100h, isoparaffin
Averagely add 7.64%, show good stability；And the Pt/SAPO-11-T catalyst prepared by comparative example 3 is in fortune
After row 50h, isomerization ability i.e. has downward trend, and the time of operation is the longest, and the inactivation of catalyst is the most obvious, and this is due to sulfur
Cover after being combined with precious metals pt on its surface, make Pt metal center inactivate, i.e. compare, prepared urging in embodiment
Agent Sulfur tolerance is higher
Can be seen that through comparative example, the non-precious metal catalyst developed in the present invention not only has the hydro carbons of excellence
Isomerization performance, and show good stability i.e. Sulfur tolerance, it is expected to become a new generation's hydrocarbon isomerization catalyst.
Claims (15)
1. a hydrocarbon isomerization non-precious metal catalyst, this catalyst is non-with supported carrier that SAPO-11 system with molecular sieve for preparing is standby
Noble metal active component is prepared from, wherein:
Described SAPO-11 molecular sieve external surface area 200-280m2/ g, in strongAcid acid amount 120-200 μm ol/g；
Described base metal active component is selected from two kinds in Ni, Mo, W, Co, on the basis of the gross weight of catalyst, with activity
The oxide meter of component metals, active component content 5～20wt% in catalyst；
Described SAPO-11 molecular sieve uses following methods to prepare:
(1) by phosphorus source, aluminum source, water, di-n-propylamine and Organic Alcohol by certain mol ratio mixing, after stirring, crystalline substance is carried out
Change, form precursor sol；
(2) in precursor sol, add cationic surfactant, organosilicon source and water, agitated, aging after carry out crystallization；
(3) solid product separated, wash, be dried, roasting, obtain SAPO-11 molecular sieve.
Catalyst the most according to claim 1, wherein, described base metal active component is Ni-Mo, Ni-W or Ni-Co
One of combination；In terms of the oxide of activity component metal, the content of metal active constituent Ni is 3-6%, the content of Mo, W or Co
For 5-8%.
Catalyst the most according to claim 1 and 2, wherein, described SAPO-11 molecular sieve is to be prepared in accordance with the following methods
Arrive:
(1) phosphorus source, aluminum source and water are mixed, and stir in the water bath with thermostatic control of 35 DEG C；Add di-n-propylamine and organic
Alcohol, loads in the rustless steel autoclave that liner is politef, under the self-generated pressure of 160 DEG C after mixing and stirring
Hydrothermal crystallizing 6h forms precursor sol；
(2) in the colloidal sol be cooled to room temperature, adding cationic surfactant, organosilicon source and water, continuing stirring until being formed
Uniform gel, and at 60 DEG C, stand aging 24h, afterwards, this gel is loaded in rustless steel autoclave, at 185-
Hydrothermal crystallizing 20-30h under the self-generated pressure of 200 DEG C；
(3) being taken out the solid product that obtain, cooled, centrifugation is also washed to neutrality, puts into baking oven in 120 DEG C of drying,
And in the Muffle furnace of 600 DEG C high-temperature roasting 5-8h, obtain SAPO-11 molecular sieve.
Catalyst the most according to claim 1 and 2, wherein, described organosilicon source: aluminum source: phosphorus source: di-n-propylamine: organic
Alcohol: cationic surfactant: the mole dosage ratio of water is (0.1-2.0): 1:(0.5-2.5): (0.7-2.0): (0.1-
50): (0.001-0.003): (20-60), wherein said organosilicon source, aluminum source and phosphorus source are respectively with SiO2、Al2O3And P2O5Meter；
Phosphorus source is selected from phosphoric acid and/or phosphorous acid, and source of aluminium is selected from boehmite and/or aluminum isopropylate., described organic
Silicon source is selected from tetraethyl orthosilicate and/or positive silicic acid propyl ester；The alcohol that described Organic Alcohol generates with the hydrolysis of described organosilicon source is identical；Institute
Stating cationic surfactant is Dodecyl trimethyl ammonium chloride.
Catalyst the most according to claim 3, wherein, described organosilicon source: aluminum source: phosphorus source: di-n-propylamine: Organic Alcohol:
Cationic surfactant: the mole dosage ratio of water is (0.1-2.0): 1:(0.5-2.5): (0.7-2.0): (0.1-50):
(0.001-0.003): (20-60), wherein said organosilicon source, aluminum source and phosphorus source are respectively with SiO2、Al2O3And P2O5Meter；
Phosphorus source is selected from phosphoric acid and/or phosphorous acid, and source of aluminium is selected from boehmite and/or aluminum isopropylate., described organic
Silicon source is selected from tetraethyl orthosilicate and/or positive silicic acid propyl ester；The alcohol that described Organic Alcohol generates with the hydrolysis of described organosilicon source is identical；Institute
Stating cationic surfactant is Dodecyl trimethyl ammonium chloride.
6. a preparation method for SAPO-11 molecular sieve, it prepares in accordance with the following methods:
(1) phosphorus source, aluminum source and water are mixed, and stir in the water bath with thermostatic control of 35 DEG C；Add di-n-propylamine and organic
Alcohol, loads in the rustless steel autoclave that liner is politef, under the self-generated pressure of 160 DEG C after mixing and stirring
Hydrothermal crystallizing 6h forms precursor sol；
(2) in the colloidal sol be cooled to room temperature, adding cationic surfactant, organosilicon source and water, continuing stirring until being formed
Uniform gel, and at 60 DEG C, stand aging 24h, afterwards, this gel is loaded in rustless steel autoclave, at 185-
Hydrothermal crystallizing 20-30h under the self-generated pressure of 200 DEG C；
(3) being taken out the solid product that obtain, cooled, centrifugation is also washed to neutrality, puts into baking oven in 120 DEG C of drying,
And in the Muffle furnace of 600 DEG C high-temperature roasting 5-8h, obtain SAPO-11 molecular sieve；
Wherein, described organosilicon source: aluminum source: phosphorus source: di-n-propylamine: Organic Alcohol: cationic surfactant: the mole dosage of water
Ratio is (0.1-2.0): 1:(0.5-2.5): (0.7-2.0): (0.1-50): (0.001-0.003): (20-60), wherein said
Organosilicon source, aluminum source and phosphorus source are respectively with SiO2、Al2O3And P2O5Meter.
Preparation method the most according to claim 6, wherein, described organosilicon source: aluminum source: phosphorus source: di-n-propylamine: organic
Alcohol: cationic surfactant: the mole dosage ratio of water is (0.1-2.0): 1:(0.5-2.5): (0.7-2.0): (0.1-
50): (0.001-0.003): (20-60), wherein said organosilicon source, aluminum source and phosphorus source are respectively with SiO2、Al2O3And P2O5Meter；
Phosphorus source is selected from phosphoric acid and/or phosphorous acid, and source of aluminium is selected from boehmite and/or aluminum isopropylate., described organic
Silicon source is selected from tetraethyl orthosilicate and/or positive silicic acid propyl ester；The alcohol that described Organic Alcohol generates with the hydrolysis of described organosilicon source is identical；Institute
Stating cationic surfactant is Dodecyl trimethyl ammonium chloride.
8. the preparation method of the non-precious metal catalyst described in any one of Claims 1 to 5, the method comprising the steps of:
(1) by described SAPO-11 molecular sieve, boehmite and sesbania powder mix homogeneously and grind, peptizer is added afterwards dilute
Salpeter solution, extruded moulding is also dried, obtains solid carrier；
(2) prepare Ni-Mo, Ni-W or Ni-Co impregnation liquid, use equi-volume impregnating by base metal activity component impregnation in
On the solid carrier being dried；
(3) be dried by the solid product obtained after dipping non-noble metal components, roasting i.e. can get described catalyst.
Method the most according to claim 8, wherein, the impregnation liquid of described Ni, Mo, W and Co can be respectively adopted Ni
(NO3)2、(NH4)6MoO24、(NH4)6H2W12O40With Co (NO3)2Solution.
The most according to claim 8 or claim 9, method, wherein, described incipient impregnation is by activity group in the way of co-impregnation
Divide and impregnated on carrier simultaneously.
The application in catalysis hydro carbons isomerization reaction of the non-precious metal catalyst described in 11. any one of Claims 1 to 5.
12. application according to claim 11, wherein, the reaction of described hydrocarbon isomerization is anti-for the double branched chain isomerization of hydro carbons
Should.
13. application according to claim 12, wherein, double that the double branched chain isomerization reaction of described hydro carbons is normal octane
Chain isomerization reaction, double branched chain isomerization reaction of normal heptane and double branched chain isomerization reaction of positive octene.
14. application according to claim 12, wherein, the double branched chain isomerization of described hydro carbons is reacted for comprising various straight chain
Double branched chain isomerization reaction of the true gasoline of hydro carbons.
The hydrocarbon isomerization method of 15. 1 kinds of non-precious metal catalysts applied described in any one of Claims 1 to 5.
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| CN109395772B (en) * | 2017-08-18 | 2021-05-11 | 中国石油大学(华东) | Isomerization catalyst and preparation method and application thereof |
| CN112337468B (en) * | 2019-08-09 | 2023-12-22 | 中国石油天然气股份有限公司 | Olefin isomerization catalyst and preparation method and application thereof |
| CN112642473A (en) * | 2019-10-12 | 2021-04-13 | 中国石油天然气股份有限公司 | Preparation method of SBA-15/ZSM-5 composite molecular sieve, catalyst and application of catalyst in double-branched-chain isomerization |
| CN111804330B (en) * | 2020-07-09 | 2023-04-25 | 中国石油大学(北京) | Sulfate radical/zirconia@SAPO-11 composite material, hydrocarbon isomerization catalyst and application |
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