CN108114743A - A kind of solid phase synthesis process of hydroisomerization catalyst - Google Patents
A kind of solid phase synthesis process of hydroisomerization catalyst Download PDFInfo
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- CN108114743A CN108114743A CN201611080327.XA CN201611080327A CN108114743A CN 108114743 A CN108114743 A CN 108114743A CN 201611080327 A CN201611080327 A CN 201611080327A CN 108114743 A CN108114743 A CN 108114743A
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- solid phase
- hydroisomerization catalyst
- synthesis process
- phase synthesis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
Abstract
The present invention provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：Step 1）, crystallization is carried out after the silicon source of solid phase, silicon source, phosphorus source template are mixed with crystal seed, gained sample is filtered, is washed, roasts 11 molecular sieves of obtained SAPO after removal phosphorus source template；Step 2）, the carried noble metal on 11 molecular sieves of SAPO, progress hydroisomerizing reaction, is made hydroisomerization catalyst after drying, roasting.Process of the present invention is simple, at low cost, efficient, and does not generate waste water, has good economic and social benefit, and during for hygrogenating isomerization reaction, the selectivity and high income of isomerization product are with a wide range of applications in domain of inorganic chemistry.
Description
Technical field
The present invention relates to domain of inorganic chemistry, more particularly to a kind of hydroisomerization catalyst under solvent-free system
Solid phase synthesis process.
Background technology
Lubricating oil is using one of extremely extensive chemical products, and low temperature flow largely influences oil product
Performance, and the low temperature flow of long-chain normal paraffin is poor, it is necessary to it is improved.Hydroisomerizing dewaxing is by the long-chain in oil product
N-alkane is converted into branched alkane by hydroisomerizing reaction, and removing part is cured, has not only reduced the pour point of base oil, but also can
Improve Viscosity Index and yield.Hydroisomerizing dewaxing has preferable superiority compared with solvent refining and CATALYTIC DEWAXING TECHNIQUE,
As the hot spot in recent petroleum refining field.On the other hand, the long-chain normal paraffin obtained by Fischer-Tropsch Synthesis is due to environment
Close friend has been to be concerned by more and more people when as oil replacement fuel oil or lubricating oil；But in such product the content of wax compared with
Height influences the using effect of product, therefore needs the n-alkane of high carbon number being converted into low pour point, low temperature stream by isomerization dewaxing
The good isohydrocarbon of dynamic property, in this process, catalyst are the cores of entire hydroisomerizing reaction.
The hygrogenating isomerization reaction of n-alkane is mainly completed on " metal -- acid " bifunctional catalyst, catalyst carrier
Acidic site isomery function is provided, metal position then provides hydrogenation/dehydrogenation function.The noble metals such as Pt/Pd have preferable hydrogenation/
Dehydrogenation, can be as the metal center of catalyst；Ten-ring the molecular sieve SAPO-11 or ZSM-22 of one-dimensional channels are due to hole
Size is smaller, there is excellent selective activization to hydroisomerizing, can be used as catalyst carrier and acid centre.Chinese patent
CN103316710A is prepared for catalyst for hydroisomerizing for F-T diesel oil hydrogenation isomeries by carrier of Si-Al molecular sieve ZSM-22
Change, when reaction pressure is 12MPa, reaction temperature is 350 DEG C, hydrogen to oil volume ratio 800, air speed 6.0h-1When, highest alkane
Isomery/positive structure is than 85.1:14.9, condensation point is -51 DEG C.Jixiang Chen etc. (Fuel Processing Technology,
2014,122(122):SAPO-11 120-128.) is used as carrier, the bifunctional catalyst prepared after carried metal nickel, tool
There is higher n-dodecane hydroisomerizing yield.Li Wei etc. (CN104525247A [P] .2015.) uses the SAPO- of multistage pore canal
11 be carrier, with one kind in Pd, Pt or Ni for active component, is prepared for meeting the boat using standard by optimizing reaction condition
Empty kerosene.Shi Difen J Millers (CN 1011593 B [P] .1991.), which use, contains silicoaluminophosphamolecular molecular sieve (such as SAPO-
11 and SAPO-41) and platinum or the catalyst of palladium hydrogenation component, it is carried out at the same time mink cell focus and is hydrocracked and isomerization reaction；It should
Process optionally prepares intermediate oil, which has good low temperature flow, suitable pour point
And viscosity.
The carrier of hydroisomerization catalyst reported above, i.e. molecular sieve, synthesis all carry out under hydrothermal conditions,
I.e. water carrys out molecular sieve needed for hydrogeneration processes isomery as solvent, should during can generate substantial amounts of waste water, cause environmental pollution；
Simultaneously as in synthesized gel rubber a large amount of water presence, the yield for causing molecular sieve is relatively low, increase production cost.Using synthesis in solid state
Method prepare molecular sieve and can preferably solve the above problems, in the synthesis process without using water or other solvents, because without producing
It gives birth to waste water and product yield is higher.Using solid phase solventless method come synthesize for hydroisomerization catalyst SAPO-11 at present still
Without report.It, will be with important application value if the stereoselectivity and yield of catalyst can be improved by this method.
The content of the invention
In view of the foregoing deficiencies of prior art, consolidating it is an object of the invention to provide a kind of hydroisomerization catalyst
Method is combined to, it is at low cost to realize that a kind of process is simple, it is efficient, and consolidating for the hydroisomerization catalyst of waste water is not generated
It is combined to method.
In order to achieve the above objects and other related objects, the present invention provides a kind of synthesis in solid state side of hydroisomerization catalyst
Method, including step：Step 1) carries out crystallization after mixing the silicon source, silicon source, template of solid phase with crystal seed, to gained sample into
SAPO-11 molecular sieves are made after removing template agent removing in row filtering, washing, roasting；Step 2) is born on the SAPO-11 molecular sieves
Supported noble metal carries out hydroisomerizing reaction after drying, roasting, hydroisomerization catalyst is made.
A kind of preferred embodiment of the solid phase synthesis process of hydroisomerization catalyst as the present invention, will be solid in step 1)
The technique that the silicon source of phase, silicon source, template are mixed with crystal seed includes ground and mixed, during ball mill mixing and pulverizer are pulverized and mixed
One kind.
A kind of preferred embodiment of the solid phase synthesis process of hydroisomerization catalyst as the present invention, it is described in step 1)
Silicon source is SiO2, silicon source Al2O3, template DPAH3PO4Or TPAH3PO4, the silicon source, silicon source, mole of plate agent
It is 0.01~0.5 than scope:1:0.2~0.9, wherein, DPA is di-n-propylamine, TPA is Tri-n-Propylamine, DPAH3PO4For two just
Propylamine and phosphatase reaction obtained solid reagent, TPAH3PO4For Tri-n-Propylamine and phosphatase reaction obtained solid reagent.
A kind of preferred embodiment of the solid phase synthesis process of hydroisomerization catalyst as the present invention, it is described in step 1)
Silicon source includes one or more kinds of mixtures in solid silicone, aerosil；Source of aluminium includes intending thin water
Aluminium stone, aluminium hydroxide, aluminum sulfate octadecahydrate, one or more kinds of mixtures of nine water aluminum nitrates；Template used is
DPA·H3PO4Or TPAH3PO4。
A kind of preferred embodiment of the solid phase synthesis process of hydroisomerization catalyst as the present invention, it is described in step 2)
The predecessor of noble metal include chloroplatinic acid, platinum nitrate, four ammonia platinum of dichloro, ammonium chloroplatinate, one or both of palladium bichloride with
On mixture.
A kind of preferred embodiment of the solid phase synthesis process of hydroisomerization catalyst as the present invention, in step 1), silicon source
Molar ratio with silicon source is 0.01~0.5:1, the molar ratio of template and silicon source is 0.2~0.9:1.
Preferably, in step 1), the molar ratio of silicon source and silicon source is 0.14~0.16:1, the molar ratio of template and silicon source
For 0.4~0.6:1.
A kind of preferred embodiment of the solid phase synthesis process of hydroisomerization catalyst as the present invention, in step 1), crystallization
Temperature range is 160~220 DEG C, when crystallization time scope is 24-72 small.
Preferably, in step 1), crystallization temperature scope is 180~200 DEG C；, when crystallization time scope is 36~48 small.
A kind of preferred embodiment of the solid phase synthesis process of hydroisomerization catalyst as the present invention, in step 1), removal
The calcination temperature scope of template is 400-700 DEG C, when roasting time scope is 2-10 small.
Preferably, in step 1), going the calcination temperature scope of template agent removing, roasting time scope is 5 for 500~550 DEG C
~6 it is small when.
A kind of preferred embodiment of the solid phase synthesis process of hydroisomerization catalyst as the present invention in step 2), passes through
Carried noble metal on SAPO-11 molecular sieves, noble-metal-supported amount are 0.1~1.0wt% described in dipping normal direction.
Preferably, in step 2), noble-metal-supported amount is 0.5~0.6wt%.
A kind of preferred embodiment of the solid phase synthesis process of hydroisomerization catalyst as the present invention, in step 2), roasting
Temperature range is 350~600 DEG C, when roasting time scope is 2~10 small.
Preferably, in step 2), calcination temperature scope is 400~500 DEG C, when roasting time scope is 4~6 small.
A kind of preferred embodiment of the solid phase synthesis process of hydroisomerization catalyst as the present invention, in step 2), hydrogenation
The range of reaction temperature of isomery is 300~600 DEG C, when reaction time range is 2~6 small.
Preferably, in step 2), the range of reaction temperature of hydroisomerizing is 350~400 DEG C, and reaction time range is 3~4
Hour.
A kind of preferred embodiment of the solid phase synthesis process of hydroisomerization catalyst as the present invention, hydroisomerizing reaction
Air pressure range is 1-6MPa, and mass space velocity scope is 0.5~4h-1, hydrogen hydrocarbon volume ratio range is 200~800:1.
As described above, the solid phase synthesis process of the hydroisomerization catalyst of the present invention, has the advantages that：
A kind of hydroisomerization catalyst method of the offer of the present invention：Sial phosphorus oxidation is prepared using the method for synthesis in solid state
Object carrier, without using solvent in carrier preparation process, for a kind of synthetic method of green high atom utilization, carried noble metal
Method is simple to operation；For isomeric compound high income during hygrogenating isomerization reaction.Process of the present invention is simple, at low cost, efficient,
And waste water is not generated, there is good economic and social benefit, during for hygrogenating isomerization reaction, the selectivity of isomerization product
And high income, it is with a wide range of applications in domain of inorganic chemistry.
Description of the drawings
Fig. 1 is shown as the XRD spectra of 1 hydroisomerization catalyst of embodiment.
Fig. 2 is shown as the stereoscan photograph of 1 hydroisomerization catalyst of embodiment.
Fig. 3 is shown as the XRD spectra of 2 hydroisomerization catalyst of embodiment.
Fig. 4 is shown as the stereoscan photograph of 2 hydroisomerization catalyst of embodiment.
Fig. 5 is shown as the XRD spectra of 3 hydroisomerization catalyst of embodiment.
Fig. 6 is shown as the stereoscan photograph of 3 hydroisomerization catalyst of embodiment.
Fig. 7 is shown as the XRD spectra of 4 hydroisomerization catalyst of embodiment.
Fig. 8 is shown as the stereoscan photograph of 4 hydroisomerization catalyst of embodiment.
Fig. 9 is shown as the XRD spectra of 5 hydroisomerization catalyst of embodiment.
Figure 10 is shown as the stereoscan photograph of 5 hydroisomerization catalyst of embodiment.
Figure 11 is shown as the stereoscan photograph of 6 hydroisomerization catalyst of embodiment.
Figure 12 is shown as the stereoscan photograph of 7 hydroisomerization catalyst of embodiment.
Figure 13 is shown as the stereoscan photograph of 8 hydroisomerization catalyst of embodiment.
Figure 14 is shown as the stereoscan photograph of 9 hydroisomerization catalyst of embodiment.
Figure 15 is shown as the stereoscan photograph of 10 hydroisomerization catalyst of embodiment.
Figure 16 is shown as the step flow diagram of the solid phase synthesis process of the hydroisomerization catalyst of the present invention.
Component label instructions
S11~S12 steps 1)~step 2)
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Please refer to Fig.1~Figure 16.It should be noted that the diagram provided in the present embodiment only illustrates this in a schematic way
The basic conception of invention, package count when only display is with related component in the present invention rather than according to actual implementation in illustrating then
Mesh, shape and size are drawn, and kenel, quantity and the ratio of each component can be a kind of random change during actual implementation, and its
Assembly layout kenel may also be increasingly complex.
As shown in figure 16, the present embodiment provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：
As shown in figure 16, step 1) S11 is carried out first, is carried out after the silicon source, silicon source, template of solid phase are mixed with crystal seed
Crystallization is filtered gained sample, washs, roasting obtained SAPO-11 molecular sieves after removal phosphorus source template.
As an example, in step 1), the technique that the silicon source, silicon source, template of solid phase are mixed with crystal seed is mixed including grinding
Close, ball mill mixing and pulverizer be pulverized and mixed in one kind.
As an example, in step 1), the silicon source is SiO2, silicon source Al2O3, template DPAH3PO4Or TPA
H3PO4, the silicon source, silicon source, the molar ratio range of template are 0.01~0.5:1:0.2~0.9, wherein, DPA is two positive third
Amine, TPA be Tri-n-Propylamine, DPAH3PO4For di-n-propylamine and phosphatase reaction obtained solid reagent, TPAH3PO4For three positive third
Amine and phosphatase reaction obtained solid reagent.
As an example, in step 1), the silicon source include in solid silicone, aerosil it is one or two kinds of with
On mixture；Source of aluminium includes boehmite, aluminium hydroxide, aluminum sulfate octadecahydrate, one kind or two of nine water aluminum nitrates
Kind or more mixture；Template used is DPAH3PO4Or TPAH3PO4。
As an example, in step 1), the molar ratio of silicon source and silicon source is 0.01~0.5:1, mole of template and silicon source
Than for 0.2~0.9:1.Preferably, it is rapid 1) in, the molar ratio of silicon source and silicon source is 0.14~0.16:1, template and silicon source
Molar ratio is 0.4~0.6:1.
As an example, in step 1), crystallization temperature scope is 160~220 DEG C, when crystallization time scope is 24-72 small.It is excellent
Selection of land, it is rapid 1) in, crystallization temperature scope be 180~200 DEG C；, when crystallization time scope is 36~48 small.
As an example, in step 1), the calcination temperature scope for removing template agent removing is 400-700 DEG C, and roasting time scope is
When 2-10 is small.Preferably, in step 1), going the calcination temperature scope of template agent removing, roasting time scope is 5 for 500~550 DEG C
~6 it is small when.
As shown in figure 16, then carry out step 2) S12, the carried noble metal on the SAPO-11 molecular sieves, through drying,
Hydroisomerizing reaction is carried out after roasting, hydroisomerization catalyst is made.
As an example, in step 2), the predecessor of the noble metal includes chloroplatinic acid, platinum nitrate, four ammonia platinum of dichloro, chlordene
Mixture more than one or both of platinic acid ammonium, palladium bichloride.
As an example, in step 2), by impregnating, carried noble metal, noble metal are born on SAPO-11 molecular sieves described in normal direction
Carrying capacity is 0.1~1.0wt%.Preferably, in step 2), noble-metal-supported amount is 0.5~0.6wt%.
As an example, in step 2), calcination temperature scope is 350~600 DEG C, when roasting time scope is 2~10 small.It is excellent
Selection of land, in step 2), calcination temperature scope is 400~500 DEG C, roasting time scope for 4~6 it is small when.
As an example, in step 2), the range of reaction temperature of hydroisomerizing is 300~600 DEG C, reaction time range 2
~6 it is small when.Preferably, in step 2), the range of reaction temperature of hydroisomerizing is 350~400 DEG C, and reaction time range is 3~4
Hour.
As an example, the air pressure range of hydroisomerizing reaction is 1-6MPa, mass space velocity scope is 0.5~4h-1, hydrogen hydrocarbon body
Product is 200~800 than scope:1.
Embodiment 1
The present embodiment provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：
Weigh 3.64g boehmites, 0.3g aerosils, 7.85g templates DPAH3PO4, 0.20g SAPO-
11 molecular sieves (crystal seed, seed) add in pulverizer and crush, solid-state reactants is made uniformly to mix.Then raw material is transferred to
It in the stainless steel autoclave of 100ml polytetrafluoroethyllining linings, and is put into baking oven, the crystallization 72h at 160 DEG C.Product with go from
Sub- water filtration washing be placed on 110 DEG C of baking ovens stand 12 it is small when.1 DEG C/min is warming up to 550 DEG C, when holding 5 is small by 20 DEG C, nature
Cooling.Obtain sample using after platinum acid chloride solution infusion process load 0.5wt%Pt at 100 DEG C it is dry 12 it is small when, it is dry after powder
It is placed in Muffle furnace and 450 DEG C of holding 4h is risen to the rate of 1 DEG C/min.Before the catalyst reaction of above-mentioned preparation under an atmosphere of hydrogen
When 400 DEG C of reduction 4 are small.Reaction pressure is 2MPa, and 320~360 DEG C of reaction temperature, hydrogen hydrocarbon volume ratio is 600, and mass space velocity is
2h-1.Three hours sampling once, replace reaction condition when stablize under corresponding conditions 12 it is small when after sample again.The present embodiment adds
Hydrogen Isomerization Results are as shown in table 1.
Attached drawing 1 is the characterization result of the XRD of 1 hydroisomerization catalyst of example, it can be seen that hydroisomerization catalyst is allusion quotation
The AEL structure of type has preferable relative crystallinity.
Attached drawing 2 is the SEM stereoscan photographs of 1 hydroisomerization catalyst of example, it can be seen that the synthesis in solid state of supporting Pt
SAPO-11 slabbings.
Embodiment 2
The present embodiment provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：
Weigh 3.64g boehmites, 0.92g aerosils, 2.53g templates DPAH3PO4, 0.20g
SAPO-11 molecular sieves (crystal seed, seed) add in pulverizer and crush, solid-state reactants is made uniformly to mix.Then raw material is shifted
It into the stainless steel autoclave of 100ml polytetrafluoroethyllining linings, and is put into baking oven, the crystallization 72h at 200 DEG C.Product is to go
Ionized water filtration washing be placed on 110 DEG C of baking ovens stand 12 it is small when.1 DEG C/min is warming up to 550 DEG C, when holding 5 is small by 20 DEG C, from
So cooling.Obtain sample using after ammonium chloroplatinate solution dipping method load 0.3wt%Pt at 100 DEG C it is dry 12 it is small when, it is dry
Powder is placed in Muffle furnace afterwards rises to 450 DEG C of holding 4h with the rate of 1 DEG C/min.In hydrogen before the catalyst reaction of above-mentioned preparation
When the lower 350 DEG C of reductase 12s of atmosphere are small.Reaction pressure is 2MPa, and 320~360 DEG C of reaction temperature, hydrogen hydrocarbon volume ratio is 600, and quality is empty
Speed is 0.5h-1.Three hours sampling once, replace reaction condition when stablize under corresponding conditions 12 it is small when after sample again.This implementation
The results are shown in Table 1 for the hydroisomerization of example.
Attached drawing 3 is the characterization result of the XRD of 2 hydroisomerization catalyst of example, it can be seen that hydroisomerization catalyst is allusion quotation
The AEL structure of type has preferable relative crystallinity.
Attached drawing 4 is the SEM stereoscan photographs of 2 hydroisomerization catalyst of example.
Embodiment 3
The present embodiment provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：
Weigh 10.92g boehmites, 0.40g aerosils, 7.40g templates DPAH3PO4, 0.20g
SAPO-11 molecular sieves (crystal seed, seed) add in pulverizer and crush, solid-state reactants is made uniformly to mix.Then raw material is shifted
It into the stainless steel autoclave of 100ml polytetrafluoroethyllining linings, and is put into baking oven, the crystallization 60h at 180 DEG C.Product is to go
Ionized water filtration washing be placed on 110 DEG C of baking ovens stand 12 it is small when.1 DEG C/min is warming up to 400 DEG C, when holding 5 is small by 20 DEG C, from
So cooling.Obtain sample using after platinum acid chloride solution infusion process load 0.6wt%Pt at 100 DEG C it is dry 12 it is small when, it is dry after powder
End is placed in Muffle furnace rises to 450 DEG C of holding 4h with the rate of 1 DEG C/min.In atmosphere of hydrogen before the catalyst reaction of above-mentioned preparation
It is lower 300 DEG C reduction 4 it is small when.Reaction pressure is 2MPa, and 320~360 DEG C of reaction temperature, hydrogen hydrocarbon volume ratio is 600, and mass space velocity is
1h-1.Three hours sampling once, replace reaction condition when stablize under corresponding conditions 12 it is small when after sample again.The present embodiment adds
Hydrogen Isomerization Results are as shown in table 1.
Attached drawing 5 is the characterization result of the XRD of 3 hydroisomerization catalyst of example, it can be seen that hydroisomerization catalyst is allusion quotation
The AEL structure of type has preferable relative crystallinity.
Attached drawing 6 is the SEM stereoscan photographs of 3 hydroisomerization catalyst of example.
Embodiment 4
The present embodiment provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：
Weigh 3.64g boehmites, 0.25g aerosils, 11.01g templates DPAH3PO4, 0.20g
SAPO-11 molecular sieves (crystal seed, seed) add in pulverizer and crush, solid-state reactants is made uniformly to mix.Then raw material is shifted
It into the stainless steel autoclave of 100ml polytetrafluoroethyllining linings, and is put into baking oven, the crystallization 60h at 180 DEG C.Product is to go
Ionized water filtration washing be placed on 110 DEG C of baking ovens stand 12 it is small when.1 DEG C/min is warming up to 550 DEG C, when holding 2 is small by 20 DEG C, from
So cooling.Obtain sample using after platinum nitrate solution infusion process load 0.6wt%Pt at 100 DEG C it is dry 12 it is small when, it is dry after powder
End is placed in Muffle furnace rises to 450 DEG C of holding 4h with the rate of 1 DEG C/min.In atmosphere of hydrogen before the catalyst reaction of above-mentioned preparation
It is lower 400 DEG C reduction 4 it is small when.Reaction pressure is 2MPa, and 320~360 DEG C of reaction temperature, hydrogen hydrocarbon volume ratio is 600, and mass space velocity is
2h-1.Three hours sampling once, replace reaction condition when stablize under corresponding conditions 12 it is small when after sample again.The present embodiment adds
Hydrogen Isomerization Results are as shown in table 1.
Attached drawing 7 is the characterization result of the XRD of 4 hydroisomerization catalyst of example, it can be seen that hydroisomerization catalyst is allusion quotation
The AEL structure of type has preferable relative crystallinity.
Attached drawing 8 is the SEM stereoscan photographs of 4 hydroisomerization catalyst of example.
Embodiment 5
The present embodiment provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：
Weigh 3.64g boehmites, 0.02g aerosils, 7.85g templates DPAH3PO4, 0.20g
SAPO-11 molecular sieves (crystal seed, seed) add in pulverizer and crush, solid-state reactants is made uniformly to mix.Then raw material is shifted
It into the stainless steel autoclave of 100ml polytetrafluoroethyllining linings, and is put into baking oven, the crystallization 60h at 190 DEG C.Product is to go
Ionized water filtration washing be placed on 110 DEG C of baking ovens stand 12 it is small when.1 DEG C/min is warming up to 500 DEG C, when holding 4 is small by 20 DEG C, from
So cooling.Obtain sample using after platinum nitrate solution infusion process load 0.5wt%Pt at 100 DEG C it is dry 12 it is small when, it is dry after powder
End is placed in Muffle furnace rises to 450 DEG C of holding 4h with the rate of 1 DEG C/min.In atmosphere of hydrogen before the catalyst reaction of above-mentioned preparation
When lower 500 DEG C of reductase 12s are small.Reaction pressure is 2MPa, and 320~360 DEG C of reaction temperature, hydrogen hydrocarbon volume ratio is 600, and mass space velocity is
0.5h-1.Three hours sampling once, replace reaction condition when stablize under corresponding conditions 12 it is small when after sample again.The present embodiment
The results are shown in Table 1 for hydroisomerization.
Attached drawing 9 is the characterization result of the XRD of 5 hydroisomerization catalyst of example, it can be seen that hydroisomerization catalyst is allusion quotation
The AEL structure of type has preferable relative crystallinity.
Attached drawing 10 is the SEM stereoscan photographs of 5 hydroisomerization catalyst of example.
Embodiment 6
The present embodiment provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：
Weigh 3.64g boehmites, 0.29g solid silicones, 7.85g templates TPAH3PO4, 0.20g SAPO-11
Molecular sieve (crystal seed, seed) adds in pulverizer and crushes, solid-state reactants is made uniformly to mix.Then raw material is transferred to 100ml
It in the stainless steel autoclave of polytetrafluoroethyllining lining, and is put into baking oven, the crystallization 48h at 200 DEG C.Product is with deionized water mistake
Filter washing be placed on 110 DEG C of baking ovens stand 12 it is small when.1 DEG C/min is warming up to 550 DEG C, when holding 10 is small by 20 DEG C, natural cooling.
Obtain sample using after platinum acid chloride solution infusion process load 0.6wt%Pt at 100 DEG C it is dry 12 it is small when, it is dry after powder be placed in horse
450 DEG C of holding 4h are not risen to the rate of 1 DEG C/min in stove.600 DEG C under an atmosphere of hydrogen before the catalyst reaction of above-mentioned preparation
Reduce 3 it is small when.Reaction pressure is 2MPa, and 320~360 DEG C of reaction temperature, hydrogen hydrocarbon volume ratio is 600, mass space velocity 1h-1.Three
Hour sampling once, replace reaction condition when stablize under corresponding conditions 12 it is small when after sample again.
Attached drawing 11 is the SEM stereoscan photographs of 6 hydroisomerization catalyst of example.
Embodiment 7
The present embodiment provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：
Weigh 3.64g boehmites, 0.45g aerosils, 8.55g templates DPAH3PO4, 0.20g
SAPO-11 molecular sieves (crystal seed, seed) add in pulverizer and crush, solid-state reactants is made uniformly to mix.Then raw material is shifted
It into the stainless steel autoclave of 100ml polytetrafluoroethyllining linings, and is put into baking oven, the crystallization 48h at 200 DEG C.Product is to go
Ionized water filtration washing be placed on 110 DEG C of baking ovens stand 12 it is small when.1 DEG C/min is warming up to 600 DEG C, when holding 5 is small by 20 DEG C, from
So cooling.Obtain sample using after platinum acid chloride solution infusion process load 0.5wt%Pt at 100 DEG C it is dry 12 it is small when, it is dry after powder
End is placed in Muffle furnace rises to 450 DEG C of holding 4h with the rate of 1 DEG C/min.In atmosphere of hydrogen before the catalyst reaction of above-mentioned preparation
It is lower 400 DEG C reduction 6 it is small when.Reaction pressure is 1MPa, and 320~360 DEG C of reaction temperature, hydrogen hydrocarbon volume ratio is 200, and mass space velocity is
2h-1.Three hours sampling once, replace reaction condition when stablize under corresponding conditions 12 it is small when after sample again.
Attached drawing 12 is the SEM stereoscan photographs of 7 hydroisomerization catalyst of example.
Embodiment 8
The present embodiment provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：
Weigh 4.00g boehmites, 0.45g aerosils, 9.00g templates DPAH3PO4, 0.20g
SAPO-11 molecular sieves (crystal seed, seed) add in pulverizer and crush, solid-state reactants is made uniformly to mix.Then raw material is shifted
It into the stainless steel autoclave of 100ml polytetrafluoroethyllining linings, and is put into baking oven, the crystallization 36h at 210 DEG C.Product is to go
Ionized water filtration washing be placed on 110 DEG C of baking ovens stand 12 it is small when.1 DEG C/min is warming up to 550 DEG C, when holding 5 is small by 20 DEG C, from
So cooling.Obtain sample using after platinum nitrate solution infusion process load 1.0wt%Pt at 100 DEG C it is dry 12 it is small when, it is dry after powder
End is placed in Muffle furnace rises to 450 DEG C of holding 4h with the rate of 1 DEG C/min.In atmosphere of hydrogen before the catalyst reaction of above-mentioned preparation
When lower 400 DEG C of reductase 12s are small.Reaction pressure is 2MPa, and 260~360 DEG C of reaction temperature, hydrogen hydrocarbon volume ratio is 400, and mass space velocity is
4h-1.Three hours sampling once, replace reaction condition when stablize under corresponding conditions 12 it is small when after sample again.
Attached drawing 13 is the SEM stereoscan photographs of 8 hydroisomerization catalyst of example.
Embodiment 9
The present embodiment provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：
Weigh 3.60g boehmites, 0.40g solid silicones, 7.85g templates TPAH3PO4, 0.20g SAPO-11
Molecular sieve (crystal seed, seed) adds in pulverizer and crushes, solid-state reactants is made uniformly to mix.Then raw material is transferred to 100ml
It in the stainless steel autoclave of polytetrafluoroethyllining lining, and is put into baking oven, the crystallization 36h at 220 DEG C.Product is with deionized water mistake
Filter washing be placed on 110 DEG C of baking ovens stand 12 it is small when.1 DEG C/min is warming up to 700 DEG C, when holding 5 is small by 20 DEG C, natural cooling.
Obtain sample using after palladium chloride solution infusion process load 0.5wt%Pd at 100 DEG C it is dry 12 it is small when, it is dry after powder be placed in horse
450 DEG C of holding 4h are not risen to the rate of 1 DEG C/min in stove.400 DEG C under an atmosphere of hydrogen before the catalyst reaction of above-mentioned preparation
Reduce 10 it is small when.Reaction pressure is 4MPa, and 320~360 DEG C of reaction temperature, hydrogen hydrocarbon volume ratio is 600, mass space velocity 2h-1.Three
Hour sampling once, replace reaction condition when stablize under corresponding conditions 12 it is small when after sample again.
Attached drawing 14 is the SEM stereoscan photographs of 9 hydroisomerization catalyst of example.
Embodiment 10
The present embodiment provides a kind of solid phase synthesis process of hydroisomerization catalyst, including step：
Weigh 3.64g boehmites, 0.80g aerosils, 7.90g templates DPAH3PO4, 0.20g
SAPO-11 molecular sieves (crystal seed, seed) add in pulverizer and crush, solid-state reactants is made uniformly to mix.Then raw material is shifted
It into the stainless steel autoclave of 100ml polytetrafluoroethyllining linings, and is put into baking oven, crystallization is for 24 hours at 220 DEG C.Product is to go
Ionized water filtration washing be placed on 110 DEG C of baking ovens stand 12 it is small when.1 DEG C/min is warming up to 550 DEG C, when holding 5 is small by 20 DEG C, from
So cooling.Obtain sample using after four ammonia platinum solution dipping method of dichloro load 0.5wt%Pt at 100 DEG C it is dry 12 it is small when, it is dry
Powder is placed in Muffle furnace afterwards rises to 450 DEG C of holding 4h with the rate of 1 DEG C/min.In hydrogen before the catalyst reaction of above-mentioned preparation
When the lower 400 DEG C of reductase 12s of atmosphere are small.Reaction pressure is 6MPa, and 280~400 DEG C of reaction temperature, hydrogen hydrocarbon volume ratio is 800, and quality is empty
Speed is 4h-1.Three hours sampling once, replace reaction condition when stablize under corresponding conditions 12 it is small when after sample again.
The SEM stereoscan photographs of 15 example of attached drawing, 10 hydroisomerization catalyst.
The hydroisomerization result of 1 Examples 1 to 5 product of table
As described above, the solid phase synthesis process of the hydroisomerization catalyst of the present invention, has the advantages that：
A kind of hydroisomerization catalyst method of the offer of the present invention：Sial phosphorus oxidation is prepared using the method for synthesis in solid state
Object carrier, without using solvent in carrier preparation process, for a kind of synthetic method of green high atom utilization, carried noble metal
Method is simple to operation；For isomeric compound high income during hygrogenating isomerization reaction.Process of the present invention is simple, at low cost, efficient,
And waste water is not generated, there is good economic and social benefit, during for hygrogenating isomerization reaction, the selectivity of isomerization product
And high income, it is with a wide range of applications in domain of inorganic chemistry.So the present invention effectively overcomes of the prior art kind
It plants shortcoming and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (18)
1. a kind of solid phase synthesis process of hydroisomerization catalyst, which is characterized in that including step：
Step 1) carries out crystallization after mixing the silicon source, silicon source, template of solid phase with crystal seed, and gained sample is filtered, is washed
It washs, roast obtained SAPO-11 molecular sieves after removal phosphorus source template；
Step 2), the carried noble metal on the SAPO-11 molecular sieves carry out hydroisomerizing reaction after drying, roasting, are made
Hydroisomerization catalyst.
2. the solid phase synthesis process of hydroisomerization catalyst according to claim 1, it is characterised in that：It, will in step 1)
The technique that the silicon source of solid phase, silicon source, template are mixed with crystal seed includes ground and mixed, and ball mill mixing and pulverizer are pulverized and mixed
In one kind.
3. the solid phase synthesis process of hydroisomerization catalyst according to claim 1, it is characterised in that：In step 1), institute
Silicon source is stated as SiO2, silicon source Al2O3, template DPAH3PO4Or TPAH3PO4, the silicon source, silicon source, phosphorus source template
The molar ratio range of agent is 0.01~0.5:1:0.2~0.9, wherein, DPA is di-n-propylamine, TPA is Tri-n-Propylamine, DPA
H3PO4For di-n-propylamine and phosphatase reaction obtained solid reagent, TPAH3PO4It is tried for Tri-n-Propylamine and phosphatase reaction obtained solid
Agent.
4. the solid phase synthesis process of hydroisomerization catalyst according to claim 1, it is characterised in that：In step 1), institute
State the mixtures for the one or more that silicon source is included in nine water sodium metasilicate, solid silicone, aerosil；The aluminium
Source includes one or more kinds of mixtures of boehmite, aluminium hydroxide, aluminum sulfate octadecahydrate, nine water aluminum nitrates；Institute
Phosphorus source template is DPAH3PO4Or TPAH3PO4。
5. the solid phase synthesis process of hydroisomerization catalyst according to claim 1, it is characterised in that：In step 2), institute
Stating the predecessor of noble metal includes one or both of chloroplatinic acid, platinum nitrate, four ammonia platinum of dichloro, ammonium chloroplatinate, palladium bichloride
Above mixture.
6. the solid phase synthesis process of hydroisomerization catalyst according to claim 1, it is characterised in that：In step 1), silicon
The molar ratio of source and silicon source is 0.01~0.5:1, the molar ratio of template and silicon source is 0.2~0.9:1.
7. the solid phase synthesis process of hydroisomerization catalyst according to claim 6, it is characterised in that：In step 1), silicon
The molar ratio of source and silicon source is 0.14~0.16:1, the molar ratio of template and silicon source is 0.4~0.6:1.
8. the solid phase synthesis process of hydroisomerization catalyst according to claim 1, it is characterised in that：It is brilliant in step 1)
It is 160~220 DEG C to change temperature range, when crystallization time scope is 24-72 small.
9. the solid phase synthesis process of hydroisomerization catalyst according to claim 8, it is characterised in that：It is brilliant in step 1)
It is 180~200 DEG C to change temperature range；, when crystallization time scope is 36~48 small.
10. the solid phase synthesis process of hydroisomerization catalyst according to claim 1, it is characterised in that：In step 1), go
The calcination temperature scope of template agent removing is 400-700 DEG C, when roasting time scope is 2-10 small.
11. the solid phase synthesis process of hydroisomerization catalyst according to claim 10, it is characterised in that：In step 1),
The calcination temperature scope of template agent removing is gone as 500~550 DEG C, when roasting time scope is 5~6 small.
12. the solid phase synthesis process of hydroisomerization catalyst according to claim 1, it is characterised in that：In step 2), lead to
Carried noble metal on SAPO-11 molecular sieves is crossed described in dipping normal direction, noble-metal-supported amount is 0.1~1.0wt%.
13. the solid phase synthesis process of hydroisomerization catalyst according to claim 12, it is characterised in that：In step 2),
Noble-metal-supported amount is 0.5~0.6wt%.
14. the solid phase synthesis process of hydroisomerization catalyst according to claim 1, it is characterised in that：In step 2), roasting
It is 350~600 DEG C to burn temperature range, when roasting time scope is 2~10 small.
15. the solid phase synthesis process of hydroisomerization catalyst according to claim 14, it is characterised in that：In step 2),
Calcination temperature scope is 400~500 DEG C, when roasting time scope is 4~6 small.
16. the solid phase synthesis process of hydroisomerization catalyst according to claim 1, it is characterised in that：In step 2), add
The range of reaction temperature of hydrogen isomery is 300~600 DEG C, when reaction time range is 2~6 small.
17. the solid phase synthesis process of hydroisomerization catalyst according to claim 16, it is characterised in that：In step 2),
The range of reaction temperature of hydroisomerizing is 350~400 DEG C, when reaction time range is 3~4 small.
18. the solid phase synthesis process of hydroisomerization catalyst according to claim 1, it is characterised in that：Hydroisomerizing is anti-
The air pressure range answered is 1-6MPa, and mass space velocity scope is 0.5~4h-1, hydrogen hydrocarbon volume ratio range is 200~800:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109879296A (en) * | 2019-04-02 | 2019-06-14 | 中国科学院上海高等研究院 | The preparation method and application of monocrystalline SAPO-11 molecular sieve, hydroisomerization catalyst |
| CN111167511A (en) * | 2019-12-18 | 2020-05-19 | 中国科学院上海高等研究院 | Preparation method of metal-loaded bifunctional catalyst |
| CN112403511A (en) * | 2020-11-26 | 2021-02-26 | 中国科学院上海高等研究院 | Preparation method of limited-domain bifunctional catalyst |
| CN115090320A (en) * | 2022-08-10 | 2022-09-23 | 中国科学院上海高等研究院 | Metal-molecular sieve bifunctional catalyst, preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879296A (en) * | 2019-04-02 | 2019-06-14 | 中国科学院上海高等研究院 | The preparation method and application of monocrystalline SAPO-11 molecular sieve, hydroisomerization catalyst |
| CN109879296B (en) * | 2019-04-02 | 2022-07-08 | 中国科学院上海高等研究院 | Preparation method and application of single crystal SAPO-11 molecular sieve and hydroisomerization catalyst |
| CN111167511A (en) * | 2019-12-18 | 2020-05-19 | 中国科学院上海高等研究院 | Preparation method of metal-loaded bifunctional catalyst |
| CN111167511B (en) * | 2019-12-18 | 2022-12-06 | 中国科学院上海高等研究院 | Preparation method of metal-loaded bifunctional catalyst |
| CN112403511A (en) * | 2020-11-26 | 2021-02-26 | 中国科学院上海高等研究院 | Preparation method of limited-domain bifunctional catalyst |
| CN115090320A (en) * | 2022-08-10 | 2022-09-23 | 中国科学院上海高等研究院 | Metal-molecular sieve bifunctional catalyst, preparation method and application thereof |
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