CN106732752B - 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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- CN106732752B CN106732752B CN201611017378.8A CN201611017378A CN106732752B CN 106732752 B CN106732752 B CN 106732752B CN 201611017378 A CN201611017378 A CN 201611017378A CN 106732752 B CN106732752 B CN 106732752B
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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 methods of C5, C6 alkane isomerization catalyst, comprising the following steps: (1) mixes modenite, inorganic binder, methylcellulose, nitric acid solution, kneading extruded moulding, by drying, roasting, obtain carrier；(2) the hydrophobicity organic amine -ol solution of carrier described in step (1) is impregnated, according to NH320%~150% molar fraction of the carrier total acid content of-TPD detection adds organic amine, and 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 detection；(4) carrier after will be dry described in step (3) carries out ion exchange with group VIII metal precursor solution, through drying, roasting, obtains catalyst.In a highly dispersed state by noble metal in the catalyst of the technology of the present invention preparation, it is distributed in catalytic inner in uniform type, which 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 fields, and in particular to a kind of preparation method of C5, C6 alkane isomerization catalyst.
Background technique
Domestic gasoline discharge standard is increasingly stringent to the restriction of alkene, aromatic hydrocarbons, and state VI gasoline discharge standard is adding at present
In tight formulation, to reduce tail gas pollution, lowering alkene, arene content in gasoline is inexorable trend.Alkene and aromatic hydrocarbons have Gaoxin
Alkane value, is important gasoline blend component, is 94 if C5 alkene is 90, C6 alkene, benzene 108, toluene 103.5, and ethylbenzene is
98.9, therefore the reduction of alkene, arene content will lead to octane number and substantially lose.Octane after positive structure C5, C6 alkane isomerization
Value is substantially improved, safety and environmental protection, is the necessary complement of the 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 by noble-metal-supported in the bifunctional catalyst on molecular sieve, and reaction temperature is 250~280
DEG C, molecular sieve is mainly modenite, and feature is that adaptability to raw material is stronger, and isomerization rate is slightly lower, needs to mention by circulation technology
High product octane number.Low form is noble metal/Cl-Al2O3The acidity of catalyst, catalyst is provided by Cl, and range of reaction temperature is
115~150 DEG C, its main feature is that isomerization rate is higher, raw material needs dehydration, sulphur, nitrogen, and impurity fluctuation easily causes catalyst inactivation, needs
Chlorine is periodically mended, equipment is easily caused to corrode.
External middle warm type catalyst is using the I-7 catalyst of Uop Inc. and the HS-10 catalyst of Shell company as representative.
In recent years, the research and development of domestic centering warm type catalyst also achieve significant progress, and middle petrochemical industry Research Institute of Petro-Chemical Engineering opens
The FI-15 type catalyst of hair put into industrial application in Zhanjiang Dongxing petrochemical industry Co., Ltd in 2 months 2001；Middle petrochemical industry Nanjing
Research institute, 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, company exploitation, 2007 Nian Yuzhong petrochemical industry Nanjing branch company 100kt/ device of the technique and mating catalyst
Upper realization industrial application.
Middle warm type C5, C6 isomerization catalyst is difunctional mechanism, and n-alkane passes through dehydrogenation-protonation-isomery rearrangement-
Deprotonation-plus hydrogen series reaction generate isoparaffin.Metal center provides hydrogenation-dehydrogenation activity, and molecular sieve acid site mentions
For protonation activity.The core technology of isomerization reaction is that acidic zeolite control and precious metal surface disperse situation: molecule
The power acid distribution that sieve is suitable for maximizes isomerization rate with proportion, reduces the loss of cracking reaction；Improve noble metal dispersion degree
Metal utilization can be increased, activity is promoted, reduce cost.
CN201410563467.7 discloses a kind of preparation method of low-carbon alkanes isomerization catalyst, it is characterized in that will live
Property component load on macropore pore creating material, obtain modified pore creating material, then will modified pore creating material and FER type small crystal grain molecular sieve, resistance to
Catalyst is made in the kneading and compactings such as molten oxide.The catalyst has two kinds of pore canal systems of different pore size, and aperture has nanometer
Grade 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, avoid deep reaction.
CN201410025582.9 discloses a kind of C5/C6 alkane isomerization catalyst, using the carrier of the beta-molecular sieve containing H
The organic hydride of Supported Co or nickel, does not add halogen and noble metal, avoids the corrosion to device, saves cost, simultaneously
Without carrying out pre- hydrogenating reduction.
A kind of preparation method of binder free titaniferous mordenite catalyst is disclosed in CN201310143464.3, by sodium
Type modenite original powder is mixed with silicon source, silicon source and alkali source, sial modenite is made 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 are made.
CN86102384A discloses a kind of new modenite prepared by aperture modenite, adsorbable kinetic diameter
Approximately more than 6.6 × 10-10The molecule of m, catalyst prepared by the zeolite are used for the isomerization of C4-C7 linear paraffin.
CN201410723154.3 discloses the preparation side of C5, C6 isomerization catalyst made of a kind of high silicon mordenite
Method is directly synthesized by an ammonium exchange, eliminates the exchange of three hypo acids and an ammonium exchange of carrier in the prior art, isomerization
It is functional.
US6198015 proposes a kind of hydroisomerization catalyst, using n-heptadecane as model compound, carries out isomerization examination
It tests, for conversion ratio up to 95%, isomerized products are selectively 70%, and catalyst carrier is made of NU-10 molecular sieve and binder.
It is respectively mentioned in US4440871, US5135638 molecular sieve carried using SAPO-11 molecular sieve and nanometer SAPO-11
Noble metal platinum, prepares alkane isomerization catalyst.
Foregoing invention has certain progress in terms of molecular sieve modified and simplified, but metal dispersion situation is not
There is improvement.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation methods of C5, C6 alkane isomerization catalyst, should
Method improves catalyst activity, reduces noble-metal-supported amount, and protect by realizing nano-dispersion of the noble metal on carrier
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 according to the present invention, including following content:
1) modenite, inorganic binder, methylcellulose, nitric acid solution are mixed, kneading extruded moulding, through overdrying
Dry, roasting, obtains carrier, and the weight content of molding post-mercerizing zeolite is 30%~95%, preferably 40%~85%.
2) the hydrophobicity organic amine -ol solution of carrier described in step 1) is impregnated, according to NH3The carrier of-TPD detection is total
20%~150% molar fraction of acid amount adds organic amine, preferably adds organic amine, leaching according to 50%~100% molar fraction
Stain liquid weight is 1.2~3 times of vehicle weight；
3) it will be dried described in step 2) with the carrier after hydrophobicity organic amine -ol solution dipping, drying temperature
Control is in NH30~100 DEG C, preferably 0~50 DEG C before and after the low temperature desorption peaks of-TPD detection；
4) by the solution of organic amine -ol described in step 3) treated carrier with group VIII metal precursor solution carry out from
Son exchange, through drying, roasts, obtains catalyst.
In the method for the present invention, the silica alumina ratio of modenite described in step 1) is 10~50:1, preferably 15~40:
1.With NH3The desorption peaks of-TPD detection are greater than 400 DEG C of acid centre, and acid centre acid of the desorption peaks greater than 400 DEG C
Amount is 0.2~3.5, preferably 0.5~3 with the ratio between the acid centre acid amount less than or equal to 400 DEG C.
In step 2), hydrophobicity organic amine be fatty amine or aromatic amine, preferably di-iso-amylamine, dihexylamine, diphenylamines or
P-phenylenediamine.
In step 4), group VIII metal is one or both of platinum, ruthenium, rhodium, osmium, palladium, iridium, ion-exchange temperature 10
~99 DEG C, the duration be 1~for 24 hours, more preferable ion-exchange temperature be 20~80 DEG C, the duration be 5~20h；Roasting temperature
Degree is 200~600 DEG C, and heating rate is 0.1~1 DEG C/min.
In the method for the present invention, inorganic binder described in step 1) is refractory oxide, is selected from boehmite, γ-
One of aluminium oxide, silica, kaolin, diatomite, zirconium oxide are a variety of, preferably boehmite and/or gamma oxidation
Aluminium, on the basis of the total weight of catalyst, the weight content of inorganic binder is 30%~90%, preferably 40%~80%.
In the method for the present invention, in step 1), on the basis of the total weight of catalyst, the weight content of methylcellulose is
1%~5%, preferably 2%~4%.
In the method for the present invention, the dip times of the hydrophobicity Amine Solutions in step 2) is 0.1~6h, preferably 0.5
~5h.Drying time is 0.5~6h, preferably 1~3h.
Catalyst shape prepared by the method for the present invention can be the existing catalyst such as strip, spherical or other special-shaped particles
Shape.
Compared with the prior art, the invention has the following advantages that
Short chain normal alkane isomerization and cracking reaction are controlled by molecular sieve acid amount and acid strength, react the main field of generation
Place strong acid center.Hydrophobicity organic amine is sufficiently combined with the acid site on modenite in the present invention, and according to carrier
NH3- TPD comes out weak acid central bare as a result, by temperature-controlled drying, then carries out ion exchange with noble metal precursor body.In this way
Strong acid center can be allowed to be protected, increase isomerization reaction activity, while because weak acid center is in conjunction with noble metal, reduce acid
Amount, inhibits cracking reaction to a certain extent.In addition, hydrophobicity organic amine and water-soluble ion exchange system poor compatibility,
The transesterification reaction rate for reducing noble metal precursor body is conducive to noble metal radial dispersion in the carrier, makes catalysis obtained
Agent is homogeneous catalyst, realizes the dispersion of nanoscale precious metal particle.There is prepared catalyst high activity, high isomery to select
The characteristics of property.In the method for the present invention, by taking load weight content is 0.3% platinum as an example, the dispersion degree of made catalyst is greater than etc.
In 90%, metal partial size is less than or equal to 1.3nm, and active component is distributed in catalyst in uniform type.
Detailed description of the invention
Fig. 1 is Z-1 carrier obtained in embodiment 1 through NH3The NH of-TPD instrument detection3Desorption figure.
Fig. 2 is Z-2 carrier obtained in embodiment 2 through NH3The NH of-TPD instrument detection3Desorption figure.
Fig. 3 is Z-3 carrier obtained in embodiment 3 through NH3The NH of-TPD instrument detection3Desorption figure.
Specific embodiment
The present invention is further illustrated 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 number | 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
Dried 1# mordenite molecular sieve 160g, boehmite 40g, methylcellulose 2g, the weight concentration is taken to be
3% dust technology 40mL, above-mentioned material is mixed, kneading extruded moulding, is warming up in 110 DEG C of dry 2h, then with 3 DEG C/min
480 DEG C, roast 3h, carrier Z-1 after being formed.
Embodiment 2
Carrier is prepared according to the method for embodiment 1, the difference is that dried 2# mordenite molecular sieve is used, it is obtained
Carrier be denoted as Z-2.
Embodiment 3
Carrier is prepared according to the method for embodiment 1, the difference is that dried 3# mordenite molecular sieve is used, it is obtained
Carrier be denoted as Z-3.
The NH of the carrier prepared in embodiment 1-33- TPD testing result is as shown in table 2, and attached drawing 1-3 is Z-1, Z-2, Z-
3 corresponding NH3Desorption peaks spectrogram.
The NH of carrier after table 2 forms3- TPD result
Embodiment 4
10g Z-3 carrier is taken, according to the total acid content in table 2, by the NH of desorption3It is corresponding with di-iso-amylamine 1:1, it needs
2.26g di-iso-amylamine prepares solution by 80% weight, i.e., dissolves 1.81g di-iso-amylamine with ethyl alcohol, it is molten to be configured to 12mL
Z-3 carrier is put into di-iso-amylamine-ethanol solution and impregnates 3h by liquid, takes out carrier and drains liquid.Than NH3It is low in-TPD
High 50 DEG C of the temperature of peak temperature is desorbed in temperature, i.e., drying carrier 1h at 267 DEG C,.Carrier after drying 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, stirring rate 120rpm, system pH
10 are maintained, swap time 18h.Catalyst is taken out after the completion of exchange, is drained away the water, is stood overnight, is warming up to 1 DEG C/min
400 DEG C, roast 4h.
Using Pt concentration of element in filtrate after inductive coupling plasma emission spectrograph detection ion exchange, instrument model
Optima 8000ICP-OES, 0.05~1.0 μ g/mL of detection limit.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 measured using 2920 chemical adsorption instrument of AutoChem of Micromeritics Instrument Corp. U.S.A
Survey device (TCD) change in detection signal.It weighs in the U-shaped glass tube that dry catalyst 0.2g is put into instrument, is blown under Ar atmosphere
10min is swept, then switches to H2- Ar gaseous mixture is warming up to 600 DEG C with 10 DEG C/min, restores catalyst completely, switch to Ar
Gas is cooled to 40 DEG C, is switched to CO-He pulse air, and start recording data complete 15 subpulses, obtain dispersion degree as a result, being shown in Table
4。
It is restored and is evaluated using fixed-bed micro-reactor, reactor lower part loads 20mL alumina ball as branch
10mL catalyst is loaded at support, middle part, and catalyst is made to be in reactor constant temperature zone, and 20mL alumina ball is loaded on top, for pre-
Heat and dispersion charging.Hydrogen reducing activated catalyst is used before evaluation, reducing condition: temperature is 240 DEG C, and Hydrogen Vapor Pressure is
1.0MPa, hydrogen flowing quantity 10L/h, reductase 12 h.Evaluation condition: 270 DEG C of reaction temperature, pressure 1.8MPa, be original with n-hexane
Material, hydrogen/hydrocarbon molar ratio are 3.0, volume space velocity 1.2h-1.Raw material and hydrogen enter reactor by reactor top, pass through from top to bottom
Catalyst bed is crossed, reaction product is analyzed using Agilent 7980B type gas-chromatography, and evaluation result is shown in Table 4.
Embodiment 5
Catalyst is prepared according to the method for embodiment 4, the difference is that organic amine used is dihexylamine, dihexylamine additive amount is
2.08g.Characterization and evaluation result are shown in Table 4.
Embodiment 6
Catalyst is prepared according to the method for embodiment 4, the difference is that Amine Solutions are diphenylamines, diphenylamines additive amount is
1.94g.Characterization and evaluation result are shown in Table 4.
Embodiment 7
Catalyst is prepared according to the method for embodiment 4, the difference is that used carrier is Z-1, organic amine used is dihexylamine,
Dihexylamine additive amount is 1.97g, and organic amine treated carrier drying temperature is 259 DEG C.Characterization and evaluation result are shown in Table 4.
Embodiment 8
Catalyst is prepared according to the method for embodiment 4, the difference is that used carrier is Z-2, organic amine used is dihexylamine,
Dihexylamine additive amount is 2.06g, and organic amine treated carrier drying temperature is 266 DEG C.Characterization and evaluation result are shown in Table 4.
Embodiment 9
Catalyst is prepared according to the method for embodiment 4, the difference is that organic amine used is diphenylamines, by the NH of desorption3With
Diphenylamines 1:1 is corresponding, needs 2.43g diphenylamines, prepares solution by 40% weight, i.e. diphenylamines additive amount is 0.97g.Characterization
And evaluation result is shown in Table 4.
Embodiment 10
Catalyst is prepared according to the method for embodiment 4, the difference is that organic amine used is diphenylamines, by the NH of desorption3With
Diphenylamines 1:1 is corresponding, needs 2.43g diphenylamines, prepares solution by 120% weight, i.e. diphenylamines additive amount is 2.92g.Table
Sign and evaluation result are shown in Table 4.
Embodiment 11
Catalyst is prepared according to the method for embodiment 4, the difference is that organic amine used is dihexylamine, dihexylamine additive amount is
2.08g, organic amine treated carrier is than NH3It is dried at a temperature of low temperature desorption peak temperature is 50 DEG C low in-TPD, is
167℃.Characterization and evaluation result are shown in Table 4.
Embodiment 12
Catalyst is prepared according to the method for embodiment 4, the difference is that organic amine used is dihexylamine, dihexylamine additive amount is
2.08g, organic amine treated carrier is than NH3It is dried at a temperature of low temperature desorption peaks in-TPD, is 217 DEG C.Characterization and
Evaluation result is shown in Table 4.
Embodiment 13
Catalyst is prepared according to the method for embodiment 4, the difference is that organic amine used is dihexylamine, dihexylamine additive amount is
2.08g, organic amine treated carrier is than NH3Low temperature is dried at a temperature of being desorbed high 100 DEG C of peak temperature in-TPD, is
317℃.Characterization and evaluation result are shown in Table 4.
Comparative example 1
Catalyst is prepared according to the method for embodiment 4, the difference is that not adding any organic amine.Characterization and evaluation result are shown in
Table 4.
Comparative example 2
Catalyst is prepared according to the method for embodiment 4, the difference is that organic amine used is dihexylamine, dihexylamine additive amount is
2.08g, organic amine treated carrier air dried overnight, without being dried.Characterization and evaluation result are shown in Table 4.
Comparative example 3
Catalyst is prepared according to the method for embodiment 4, the difference is that organic amine used is dihexylamine, dihexylamine additive amount is
The organic amine processed carrier tetraammineplatinum chloride solution of 5.5g 0.03g containing Pt is impregnated 18h by 2.08g, the solution
PH value is 10.Characterization and evaluation result are shown in Table 4.
The catalyst preparation conditions of above-described embodiment 4-13 and comparative example 1-3 are shown in Table 3.
3 catalyst preparation conditions of table
A indicates the molar ratio of organic amine additive amount and carrier total acid content in table 3；△ T indicate carrier drying temperature relative to
Carrier NH3The temperature of low temperature desorption peaks in-TPD testing result.
The characterization and evaluation result of 4 catalyst of table
Isomerization rate and isomerisation selectivity in table 4 calculate (weight percent) as follows:
C6 alkane total content × 100% in isomerization rate=isomery C6 content/product
C6 alkane total content × 100% in isomerisation selectivity=2,2- dimethylbutane content/product.
From the results shown in Table 4, the catalyst prepared using the method for the invention, noble metal dispersion degree are reached
90% or more, it is handled compared in comparative example without organic amine, does not carry out carrier temperature-controlled drying, and ion after molding is not used
The catalyst of exchange process, the catalyst performance prepared by the method for the invention is more preferable, conversion ratio, isomerization rate and isomerization
Selectivity is above comparative example catalyst.
In the method for the present invention, by taking load weight content is 0.3% platinum as an example, the dispersion degree of made catalyst is more than or equal to
90%, active component is distributed in catalyst in uniform type.
Claims (5)
1. a kind of preparation method of C5, C6 alkane isomerization catalyst, it is characterised in that the following steps are included:
1) modenite, inorganic binder, methylcellulose, nitric acid solution are mixed, kneading extruded moulding, by drying, roasting
It burns, obtains carrier, the weight content of molding post-mercerizing zeolite is 30%~95%；
2) the hydrophobicity organic amine -ol solution of carrier described in step 1) is impregnated, according to NH3The carrier total acid content of-TPD detection
20%~150% molar fraction add organic amine, maceration extract weight is 1.2~3 times of vehicle weight；The hydrophobicity has
Machine amine is di-iso-amylamine, dihexylamine, diphenylamines or p-phenylenediamine；
3) it will be dried described in step 2) with the carrier after hydrophobicity organic amine -ol solution dipping, drying temperature control
In NH3Within the temperature range of -50 DEG C to+100 DEG C of low temperature desorption peaks of-TPD detection；
4) carrier after will be dry described in step 3) carries out ion exchange with group VIII metal precursor solution, through drying, roasting
It burns, obtains catalyst, the maturing temperature is 400~600 DEG C, and heating rate is 0.1~1 DEG C/min.
2. preparation method described in accordance with the claim 1, which is characterized in that in step 1), the SiO of the modenite2With
Al2O3Molar ratio be 10~50:1, have NH3The desorption peaks of-TPD detection are greater than 400 DEG C of acid centre, and desorption peaks
Acid centre acid amount greater than 400 DEG C and the ratio between the acid centre acid amount less than or equal to 400 DEG C are 0.2~3.5.
3. preparation method described in accordance with the claim 1, which is characterized in that in step 2), according to NH3The carrier of-TPD detection is total
50%~100% molar fraction of acid amount adds organic amine.
4. preparation method described in accordance with the claim 1, which is characterized in that in step 3), drying temperature is controlled in NH3- TPD inspection
Within the temperature range of -50 DEG C to+50 DEG C of low temperature desorption peaks of survey.
5. preparation method described in accordance with the claim 1, which is characterized in that in step 4), group VIII metal be platinum, ruthenium, rhodium,
One or both of osmium, palladium, iridium, ion-exchange temperature be 10~99 DEG C, the duration be 1~for 24 hours.
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|---|---|---|---|---|
| CN101397230A (en) * | 2007-09-28 | 2009-04-01 | 中国石油化工股份有限公司 | C5 and/or C6 alkane isomerization process |
| 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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