CN106732752A - A kind of preparation method of C5, C6 alkane isomerization catalyst - Google Patents
A kind of preparation method of C5, C6 alkane isomerization catalyst Download PDFInfo
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- CN106732752A CN106732752A CN201611017378.8A CN201611017378A CN106732752A CN 106732752 A CN106732752 A CN 106732752A CN 201611017378 A CN201611017378 A CN 201611017378A CN 106732752 A CN106732752 A CN 106732752A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/22—Noble metals
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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
- C10G45/62—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 platinum group metals or compounds thereof
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
The present invention relates to a kind of preparation method of C5, C6 alkane isomerization catalyst, comprise the following steps：(1) modenite, inorganic binder, methylcellulose, salpeter solution are mixed, kneading extruded moulding, by drying, roasting, obtains carrier；(2) carrier described in step (1) is impregnated with hydrophobicity organic amine alcoholic solution, according to NH320%~150% molar fraction addition organic amine of the carrier total acid content of TPD detections, maceration extract weight is 1.2~3 times of vehicle weight；(3) carrier after dipping is dried, drying temperature is controlled in NH30~100 DEG C before and after the low temperature desorption peaks of TPD detections；(4) dried carrier described in step (3) is carried out into ion exchange with group VIII metal precursor solution, through drying, roasting, obtains catalyst.By noble metal in catalyst prepared by the technology of the present invention in a highly dispersed state, it is distributed in uniform type in catalytic inner, the catalyst reacts for C5, C6 alkane isomerization, and n-alkane high conversion rate, isomerisation selectivity are good.
Description
Technical field
The present invention relates to catalyst field, and in particular to a kind of preparation method of C5, C6 alkane isomerization catalyst.
Background technology
Restriction of the domestic gasoline discharge standard to alkene, aromatic hydrocarbons is increasingly strict, and current state VI gasoline discharge standards add
It is to reduce tail gas pollution in tight formulation, alkene, arene content are inexorable trends in downward gasoline.Alkene and aromatic hydrocarbons have Gaoxin
Alkane value, is important gasoline blend component, and such as C5 alkene is that 90, C6 alkene is 94, and benzene is 108, and toluene is 103.5, and ethylbenzene is
98.9, therefore the reduction of alkene, arene content will cause octane number significantly to lose.Octane after positive structure C5, C6 alkane isomerization
Value is substantially improved, safety and environmental protection, is the necessary complement of following gasoline blend component.
According to operating condition, alkane isomerization catalyst is divided into high temperature modification, middle warm type, low form.High temperature modification is selected because of product
Selecting property is poor, has eliminated.Middle warm type is that reaction temperature is 250~280 in the bifunctional catalyst on molecular sieve by noble-metal-supported
DEG C, molecular sieve is mainly modenite, and feature is stronger adaptability to raw material, and isomerization rate is lower slightly, it is necessary to be carried by circulation technology
High product octane number.Low form is noble metal/Cl-Al2O3Catalyst, the acid of catalyst is provided by Cl, and range of reaction temperature is
115~150 DEG C, it is characterized in that isomerization rate is higher, raw material needs dehydration, sulphur, nitrogen, impurity fluctuation easily causes catalyst inactivation, needs
Chlorine is periodically mended, equipment corrosion is easily caused.
External middle warm type catalyst is with the HS-10 catalyst of the I-7 catalyst of Uop Inc. and Shell companies as representative.
In recent years, the research and development of domestic centering warm type catalyst also achieve significant progress, and sinopec Research Institute of Petro-Chemical Engineering opens
The FI-15 types catalyst of hair put into commercial Application in 2 months 2001 in Zhanjiang Dongxing petrochemical industry Co., Ltd；Sinopec Nanjing
Research institute of branch company, East China University of Science and Beijing designing institute have developed jointly C5, C6 isomerization technique, and catalyst is Nanjing point
The CI-50 of research institute of company exploitation, the technique and supporting catalyst 2007 are in sinopec Nanjing branch company 100kt/ devices
On realize commercial Application.
Middle warm type C5, C6 isomerization catalyst is difunctional mechanism, n-alkane by dehydrogenation-protonation-isomery rearrangement-
Deprotonation-hydrogenation series reaction generation isoparaffin.Metal center provides hydrogenation-dehydrogenation activity, and molecular sieve acid site carries
For protonation activity.The core technology of isomerization reaction is that acidic zeolite control and precious metal surface disperse situation：Molecule
The suitable power acid distribution of sieve maximizes isomerization rate with proportioning, reduces the loss of cracking reaction；Improve noble metal dispersion degree
Rate of metal, lifting activity, reduces cost can be increased.
CN201410563467.7 discloses a kind of preparation method of low-carbon alkanes isomerization catalyst, it is characterized in that will be living
Property component load on macropore pore creating material, obtain modified pore creating material, then by modified pore creating material and FER types small crystal grain molecular sieve, resistance to
The kneading and compactings such as molten oxide are obtained catalyst.The catalyst has two kinds of pore canal systems of different pore size, and aperture has nanometer
Level size, is substantially carried out the reaction of linear paraffin molecular isomerism, and macropore is manufactured by pore creating material, for improving reactant and product
Diffusion velocity, it is to avoid deep reaction.
CN201410025582.9 discloses a kind of C5/C6 alkane isomerization catalysts, using the carrier containing H beta-molecular sieves
The organic hydride of Supported Co or nickel, without halogen and noble metal, it is to avoid corrosion to device, saves cost, while
Pre- hydrogenating reduction need not be carried out.
A kind of preparation method of binder free titaniferous mordenite catalyst is disclosed in CN201310143464.3, by sodium
Type modenite original powder mixes with silicon source, silicon source and alkali source, sial modenite is obtained using dry gum method, then sial mercerising is boiled
Stone is exchanged with ammonium, pickling dealuminzation and gas phase mend titanium and binder free titaniferous mercerising molecular sieve catalyst is obtained.
CN86102384A discloses a kind of new modenite prepared by aperture modenite, adsorbable kinetic diameter
Approximately more than 6.6 × 10-10The molecule of m, the catalyst prepared by the zeolite is used for the isomerization of C4-C7 linear paraffins.
CN201410723154.3 discloses the preparation side of C5, C6 isomerization catalyst that a kind of high silicon mordenite is made
Method, is exchanged by an ammonium and is directly synthesized, and three hypo acids for eliminating carrier in the prior art are exchanged and an ammonium exchange, isomerization
It is functional.
US6198015 proposes a kind of hydroisomerization catalyst, with n-heptadecane as model compound, carries out isomerization examination
Test, up to 95%, isomerized products are selectively 70% to conversion ratio, and catalyst carrier is made up of NU-10 molecular sieves and binding agent.
It is respectively mentioned in US4440871, US5135638 molecular sieve carried using SAPO-11 molecular sieves and nanometer SAPO-11
Noble metal platinum, prepares alkane isomerization catalyst.
Foregoing invention has certain progress at aspects such as molecular sieve modified and simplified preparation processes, but metal dispersion situation is not
There is improvement.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of preparation method of C5, C6 alkane isomerization catalyst, should
Method is disperseed by realizing nanoscale of the noble metal on carrier, improves catalyst activity, reduces noble-metal-supported amount, and protect
The activity in molecular sieve acid site is stayed, preparation method is simple, and process costs are low.
The preparation method of C5, C6 alkane isomerization catalyst involved in the present invention, including following content：
1) modenite, inorganic binder, methylcellulose, salpeter solution are mixed, kneading extruded moulding, through overdrying
Dry, roasting, obtains carrier, and the weight content for being molded post-mercerizing zeolite is 30%~95%, preferably 40%~85%.
2) by step 1) described in carrier hydrophobicity organic amine -ol solution impregnation, according to NH3The carrier of-TPD detections is total
20%~150% molar fraction addition organic amine of acid amount, preferably adds organic amine, leaching according to 50%~100% molar fraction
Stain liquid weight is 1.2~3 times of vehicle weight；
3) by step 2) described in be dried with the carrier after hydrophobicity organic amine -ol solution impregnation, drying temperature
Control is in NH30~100 DEG C, preferably 0~50 DEG C before and after the low temperature desorption peaks of-TPD detections；
4) by step 3) described in organic amine -ol solution treatment after carrier carried out with group VIII metal precursor solution from
Son is exchanged, and through drying, is calcined, is obtained catalyst.
In the inventive method, step 1) described in the silica alumina ratio of modenite be 10~50:1, preferably 15~40:
1.With NH3The acid centre of the desorption peaks more than 400 DEG C of-TPD detections, and acid centre acid of the desorption peaks more than 400 DEG C
The ratio between amount and the acid amount of the acid centre less than or equal to 400 DEG C are 0.2~3.5, preferably 0.5~3.
Step 2) in, hydrophobicity organic amine be fatty amine or aromatic amine, preferably di-iso-amylamine, dihexylamine, diphenylamines or
P-phenylenediamine.
Step 4) in, group VIII metal be platinum, ruthenium, rhodium, osmium, palladium, iridium in one or two, ion-exchange temperature is 10
~99 DEG C, the duration is 1~24h, and more preferably ion-exchange temperature is 20~80 DEG C, and the duration is 5~20h；Roasting temperature
It is 200~600 DEG C to spend, and heating rate is 0.1~1 DEG C/min.
In the inventive method, step 1) described in inorganic binder be refractory oxide, selected from boehmite, γ-
One or more in aluminum oxide, silica, kaolin, diatomite, zirconium oxide, preferably boehmite and/or gamma oxidation
Aluminium, on the basis of the gross weight of catalyst, the weight content of inorganic binder is 30%~90%, preferably 40%~80%.
In the inventive method, step 1) in, on the basis of the gross weight of catalyst, the weight content of methylcellulose is
1%~5%, preferably 2%~4%.
In the inventive method, step 2) in the dip time of hydrophobicity Amine Solutions be 0.1~6h, preferably 0.5
~5h.Drying time is 0.5~6h, preferably 1~3h.
Catalyst shape prepared by the inventive method can be the existing catalyst such as strip, spherical or other special-shaped particles
Shape.
Compared with the prior art, the present invention has advantages below：
Short chain normal alkane isomerization and cracking reaction are reacted the main field for occurring by molecular sieve acid amount and acid strength control
Place strong acid center.Hydrophobicity organic amine is fully combined with the acid site on modenite in the present invention, and according to carrier
NH3- TPD results, by temperature-controlled drying, make weak acid central bare out, then carry out ion exchange with noble metal precursor body.So
Strong acid center can be allowed to be protected, increase isomerization reaction activity, while because weak acid center is combined with noble metal, reducing acid
Amount, inhibits cracking reaction to a certain extent.Additionally, hydrophobicity organic amine and water miscible ion exchange system poor compatibility,
The transesterification reaction rate of noble metal precursor body is reduced, is conducive to the dispersion of noble metal radial direction in the carrier, make obtained catalysis
Agent is homogeneous catalyst, realizes that nanoscale precious metal particle disperses.There is prepared catalyst high activity, isomery high to select
The characteristics of property.In the inventive method, by taking the platinum that load weight content is 0.3% as an example, the decentralization of made catalyst more than etc.
In 90%, metal particle diameter is less than or equal to 1.3nm, and active component is distributed in catalyst in uniform type.
Brief description of the drawings
Fig. 1 be embodiment 1 in obtained Z-1 carriers through NH3The NH of-TPD instruments detection3Desorption figure.
Fig. 2 be embodiment 2 in obtained Z-2 carriers through NH3The NH of-TPD instruments detection3Desorption figure.
Fig. 3 be embodiment 3 in obtained Z-3 carriers through NH3The NH of-TPD instruments detection3Desorption figure.
Specific embodiment
The present invention is further explained below by embodiment, but the present invention is not only limited in this.
Used mordenite molecular sieve is commercially available hydrogen type molecular sieve in embodiment, and property is as shown in table 1.
The commercially available mordenite molecular sieve property of table 1
| Modenite is numbered | 1# | 2# | 3# |
| SiO2/Al2O3 | 16 | 27 | 35 |
| Specific surface area, m2/g | 401 | 422 | 432 |
| Pore volume, mL/g | 0.2326 | 0.2739 | 0.3010 |
| Average pore size, nm | 2.31 | 2.57 | 2.92 |
| Na2O, wt% | 0.03 | 0.05 | 0.04 |
Embodiment 1
Taking dried 1# mordenite molecular sieves 160g, boehmite 40g, methylcellulose 2g, weight concentration is
3% dust technology 40mL, above-mentioned material is mixed, and kneading extruded moulding dries 2h at 110 DEG C, then be warming up to 3 DEG C/min
480 DEG C, it is calcined 3h, carrier Z-1 after being molded.
Embodiment 2
Method according to embodiment 1 prepares carrier, the difference is that dried 2# mordenite molecular sieves are used, it is obtained
Carrier be designated as Z-2.
Embodiment 3
Method according to embodiment 1 prepares carrier, the difference is that dried 3# mordenite molecular sieves are used, it is obtained
Carrier be designated as Z-3.
The NH of the carrier prepared in embodiment 1-33As shown in table 2, accompanying drawing 1-3 is Z-1, Z-2, Z- to-TPD testing results
3 corresponding NH3Desorption peaks spectrogram.
The NH of carrier after the shaping of table 23- TPD results
Embodiment 4
10g Z-3 carriers are taken, according to the total acid content in table 2, by the NH of desorption3With di-iso-amylamine 1:1 correspondence, it is necessary to
2.26g di-iso-amylamines, by 80% weight prepare solution, will 1.81g di-iso-amylamines ethanol dissolving, be configured to 12mL molten
Liquid, Z-3 carriers is put into 3h is impregnated in di-iso-amylamine-ethanol solution, is taken out carrier and is drained liquid.Than NH3It is low in-TPD
The temperature of temperature 50 DEG C high of peak temperature of desorption, i.e., dry carrier 1h at 267 DEG C,.Dried carrier is put into 350g containing 0.03g
Ion exchange is carried out in the tetraammineplatinum chloride aqueous solution of Pt, exchange temperature is 75 DEG C, and stir speed (S.S.) is 120rpm, system pH
10 are maintained, swap time is 18h.Catalyst is taken out after the completion of exchange, is drained away the water, stood overnight, be warming up to 1 DEG C/min
400 DEG C, it is calcined 4h.
Using Pt concentration of element, INSTRUMENT MODEL in filtrate after inductive coupling plasma emission spectrograph detection ion exchange
Optima 8000ICP-OES, the μ g/mL of detection limit 0.05~1.0.Pt load capacity on catalyst is calculated according to data measured, as a result
It is shown in Table 4.
Metal dispersity, conductance cell inspection are determined using the chemical adsorption instruments of AutoChem 2920 of Micromeritics Instrument Corp. U.S.A
Survey device (TCD) change in detection signal.Weigh in the U-shaped glass tube during dry catalyst 0.2g is put into instrument, blown under Ar atmosphere
10min is swept, then switches to H2- Ar gaseous mixtures, 600 DEG C are warming up to 10 DEG C/min, catalyst is reduced completely, switch to Ar
Gas, is cooled to 40 DEG C, switches to CO-He pulse airs, and start recording data complete 15 subpulses, obtain decentralization result, are shown in Table
4。
Reduced using fixed-bed micro-reactor and evaluated, reactor lower part is loaded 20mL alumina balls as branch
Support, middle part filling 10mL catalyst makes catalyst be in reactor constant temperature zone, top filling 20mL alumina balls, for pre-
Heat and dispersion feed.Hydrogen reducing activated catalyst, reducing condition are used before evaluating：Temperature is 240 DEG C, and Hydrogen Vapor Pressure is
1.0MPa, hydrogen flowing quantity is 10L/h, reductase 12 h.Appreciation condition：270 DEG C of reaction temperature, pressure 1.8MPa, with n-hexane as former
Material, hydrogen/hydrocarbon mol ratio is 3.0, volume space velocity 1.2h-1.Raw material and hydrogen enter reactor by reactor top, pass through from top to bottom
Beds are crossed, product is analyzed using Agilent 7980B type gas-chromatographies, and evaluation result is shown in Table 4.
Embodiment 5
Method according to embodiment 4 prepares catalyst, the difference is that organic amine used is dihexylamine, dihexylamine addition is
2.08g.Characterize and evaluation result is shown in Table 4.
Embodiment 6
Method according to embodiment 4 prepares catalyst, the difference is that Amine Solutions are diphenylamines, diphenylamines addition is
1.94g.Characterize and evaluation result is shown in Table 4.
Embodiment 7
Method according to embodiment 4 prepares catalyst, the difference is that used carrier is Z-1, organic amine used is dihexylamine,
Dihexylamine addition is 1.97g, and the carrier drying temperature after organic amine treatment is 259 DEG C.Characterize and evaluation result is shown in Table 4.
Embodiment 8
Method according to embodiment 4 prepares catalyst, the difference is that used carrier is Z-2, organic amine used is dihexylamine,
Dihexylamine addition is 2.06g, and the carrier drying temperature after organic amine treatment is 266 DEG C.Characterize and evaluation result is shown in Table 4.
Embodiment 9
Method according to embodiment 4 prepares catalyst, the difference is that organic amine used is diphenylamines, by the NH of desorption3With
Diphenylamines 1:1 correspondence is, it is necessary to 2.43g diphenylamines, it is 0.97g to prepare solution, i.e. diphenylamines addition by 40% weight.Characterize
And evaluation result is shown in Table 4.
Embodiment 10
Method according to embodiment 4 prepares catalyst, the difference is that organic amine used is diphenylamines, by the NH of desorption3With
Diphenylamines 1:1 correspondence is, it is necessary to 2.43g diphenylamines, it is 2.92g to prepare solution, i.e. diphenylamines addition by 120% weight.Table
Levy and evaluation result is shown in Table 4.
Embodiment 11
Method according to embodiment 4 prepares catalyst, the difference is that organic amine used is dihexylamine, dihexylamine addition is
2.08g, the carrier after organic amine treatment is than NH3It is dried at a temperature of low 50 DEG C of peak temperature of low temperature desorption in-TPD, is
167℃.Characterize and evaluation result is shown in Table 4.
Embodiment 12
Method according to embodiment 4 prepares catalyst, the difference is that organic amine used is dihexylamine, dihexylamine addition is
2.08g, the carrier after organic amine treatment is than NH3It is dried at a temperature of low temperature desorption peaks in-TPD, is 217 DEG C.Characterize and
Evaluation result is shown in Table 4.
Embodiment 13
Method according to embodiment 4 prepares catalyst, the difference is that organic amine used is dihexylamine, dihexylamine addition is
2.08g, the carrier after organic amine treatment is than NH3It is dried at a temperature of 100 DEG C high of peak temperature of low temperature desorption in-TPD, is
317℃.Characterize and evaluation result is shown in Table 4.
Comparative example 1
Method according to embodiment 4 prepares catalyst, the difference is that without any organic amine.Characterize and evaluation result is shown in
Table 4.
Comparative example 2
Method according to embodiment 4 prepares catalyst, the difference is that organic amine used is dihexylamine, dihexylamine addition is
2.08g, the carrier air dried overnight after organic amine treatment, treatment is not dried.Characterize and evaluation result is shown in Table 4.
Comparative example 3
Method according to embodiment 4 prepares catalyst, the difference is that organic amine used is dihexylamine, dihexylamine addition is
2.08g, the carrier that organic amine is treated tetraammineplatinum chloride solution impregnation 18hs of the 5.5g containing Pt 0.03g, the solution
PH value is 10.Characterize and evaluation result is shown in Table 4.
The catalyst preparation conditions of above-described embodiment 4-13 and comparative example 1-3 are shown in Table 3.
The catalyst preparation conditions of table 3
A represents the mol ratio of organic amine addition and carrier total acid content in table 3；△ T represent carrier drying temperature relative to
Carrier NH3The temperature of low temperature desorption peaks in-TPD testing results.
The sign and evaluation result of the catalyst of table 4
Isomerization rate and isomerisation selectivity in table 4 are calculated (percentage by weight) as follows：
C6 alkane total content × 100% in isomerization rate=isomery C6 contents/product
C6 alkane total content × 100% in isomerisation selectivity=2,2- dimethylbutanes content/product.
From the results shown in Table 4, the catalyst for being prepared using the method for the invention, noble metal dispersion degree is reached
More than 90%, processed without organic amine compared in comparative example, carrier temperature-controlled drying is not carried out, and ion after shaping is not used
The catalyst of exchange process, the catalyst performance prepared by the method for the invention is more preferable, its conversion ratio, isomerization rate and isomerization
Selectivity is above comparative example catalyst.
In the inventive method, by taking the platinum that load weight content is 0.3% as an example, the decentralization of made catalyst is more than or equal to
90%, active component is distributed in catalyst in uniform type.
Claims (8)
1. a kind of preparation method of C5, C6 alkane isomerization catalyst, it is characterised in that comprise the following steps：
1) modenite, inorganic binder, methylcellulose, salpeter solution are mixed, kneading extruded moulding, by drying, roasting
Burn, obtain carrier, the weight content for being molded post-mercerizing zeolite is 30%~95%；
2) by step 1) described in carrier hydrophobicity organic amine -ol solution impregnation, according to NH3The carrier total acid content of-TPD detections
20%~150% molar fraction addition organic amine, maceration extract weight is 1.2~3 times of vehicle weight；
3) by step 2) described in be dried with the carrier after hydrophobicity organic amine -ol solution impregnation, drying temperature control
In NH30~100 DEG C before and after the low temperature desorption peaks of-TPD detections；
4) by step 3) described in dried carrier carry out ion exchange with group VIII metal precursor solution, through drying, roasting
Burn, obtain catalyst.
2. according to the preparation method described in claim 1, it is characterised in that step 1) in, the sial mole of the modenite
Than being 10~50:1, with NH3The acid centre of the desorption peaks more than 400 DEG C of-TPD detections, and desorption peaks are more than 400 DEG C
The ratio between acid centre acid amount and the acid amount of the acid centre less than or equal to 400 DEG C are 0.2~3.5.
3. according to the preparation method described in claim 1, it is characterised in that step 2) in, hydrophobicity organic amine be fatty amine or
Aromatic amine.
4. according to the preparation method described in claim 3, it is characterised in that described hydrophobicity organic amine is di-iso-amylamine, two
Hexylamine, diphenylamines or p-phenylenediamine.
5. according to the preparation method described in claim 1, it is characterised in that step 2) in, according to NH3The carrier of-TPD detections is total
50%~100% molar fraction addition organic amine of acid amount.
6. according to the preparation method described in claim 1, it is characterised in that step 3) in, drying temperature is controlled in NH3- TPD is examined
0~50 DEG C before and after the low temperature desorption peaks of survey.
7. according to the preparation method described in claim 1, it is characterised in that step 4) in, group VIII metal be platinum, ruthenium, rhodium,
One or two in osmium, palladium, iridium, ion-exchange temperature is 10~99 DEG C, and the duration is 1~24h.
8. according to the preparation method described in claim 1, it is characterised in that step 4) in, sintering temperature is 200~600 DEG C, is risen
Warm speed is 0.1~1 DEG C/min.
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Cited By (2)
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|---|---|---|---|---|
| CN110369001A (en) * | 2018-04-12 | 2019-10-25 | 中国科学院大连化学物理研究所 | A method of preparing high-dispersion metal catalyst |
| EP3744424A4 (en) * | 2018-01-26 | 2021-11-03 | Dalian Institute of Chemical Physics, Chinese Academy of Sciences | Organic base modified composite catalyst and method for preparing ethylene by means of hydrogenation of carbon monoxide |
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| CN105214717A (en) * | 2015-10-22 | 2016-01-06 | 中国海洋石油总公司 | A kind of preparation method of lube base oil isomerization dewaxing catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3744424A4 (en) * | 2018-01-26 | 2021-11-03 | Dalian Institute of Chemical Physics, Chinese Academy of Sciences | Organic base modified composite catalyst and method for preparing ethylene by means of hydrogenation of carbon monoxide |
| CN110369001A (en) * | 2018-04-12 | 2019-10-25 | 中国科学院大连化学物理研究所 | A method of preparing high-dispersion metal catalyst |
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